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Study of Homogeneous and Heterogenized Ruthenium / Tin Heterobimetallic Complexes: Synthesis, Electrochemistry and Catal...


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STUDY OF HOMOGENEOUS AND HETEROGENIZED RUTHENIUM / TIN HETEROBIMETALLIC COMPLEXES: SYNTHESIS, ELECTROCHEMISTRY AND CATALYTIC PROPERTIES By COREY R. ANTHONY A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2006

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Copyright 2006 by Corey R. Anthony

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This dissertation is dedicated to my grandfather, Leonard Legister, September 30th, 1900 – March 4th, 2004. You may be gone POPPA but you will never be forgotten.

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iv ACKNOWLEDGMENTS I would like to first thank God because with him all things are possible. I would now like to acknowledge the strong women who have had a positive impact in my life. First and foremost I th ank my mother, a remarkable single parent who made countless sacrifices in raising three ch ildren. To her I owe my strong work ethic, drive for education and will always love unc onditionally. I want to also acknowledge my lovely wife for all her love, support and pa tience which kept me focused during many endless nights of research. To her I owe a tremendous debt of gratitude for being my rock these last two years. I also wish to thank my sisters Charmaine and Cheryl and my cousin Heather for always being there and ma king this PhD dream of mine a reality. I would now like to thank my advisor, another strong woman Dr. Lisa McElweeWhite. To her I express gratitude for all th e discussions and advice during the six years I have apprenticed with her. Under her tutela ge I was able to grow both as a chemist and as a person. I’d like to also thank the McEl wee-White group members past and present. Special thanks from me go out to Dr. Ke isha-Gay Hylton, Dr. Corey Wilder, Dr. Ying Yang and Daniel Serra. I would also like to thank Dr. Khalil Abboud for solving the Xray crystal structures presen ted in this dissertation.

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v TABLE OF CONTENTS page ACKNOWLEDGMENTS.................................................................................................iv LIST OF TABLES...........................................................................................................viii LIST OF FIGURES.............................................................................................................x ABSTRACT......................................................................................................................x ii CHAPTER 1 LITERATURE REVIEW.............................................................................................1 Oxidation of Organic Molecules..................................................................................1 Oxidation of Alcohols...........................................................................................2 Electrochemical Oxidation of Methanol in Fuel Cells.................................................3 Mechanism............................................................................................................4 Binary Electrocatalysts..........................................................................................6 Pt/Ru binary anodes.......................................................................................7 Combinatorial Screening.......................................................................................8 Reaction Intermediates..........................................................................................8 Electrochemical Oxidation of Alcohols by Metal Complexes.....................................9 Ruthenium Electrocatalysts.................................................................................11 Reactivity of Bime tallic Complexes...........................................................................13 Heterobimetallic Electr ooxidation Catalysts..............................................................16 Product Formation...............................................................................................18 Bulk Electrolysis of Methanol.............................................................................20 Summary.....................................................................................................................21 2 SYNTHESIS AND ELECTROCHEMICAL PROPERTIES OF A RUTHENIUM / MERCURY HETEROBIMETALLIC COMPLEX...................................................22 Introduction.................................................................................................................22 Role of the Non-Ru Metal Center.......................................................................25 Lewis Acid Catalysts..................................................................................................27 Classification of Lewis Acids..............................................................................29 Lewis Acidic Properties of Mercury Complexes................................................31 Chemistry of Mercury.................................................................................................33

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vi Mercury Catalyzed Reactions..............................................................................33 Synthesis and Characterization of CpRu(PPh3)(-Cl)(-dppm)HgCl2......................34 Attempted Synthesis of CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 )........................34 Synthesis of CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 )..........................................36 Synthesis of CpRu(PPh3)(-Cl)(-dppm)Hg(OAc)2 ( 18 )...................................36 Analysis of CpRu(PPh3)(-Cl)(-dppm)HgCl2 Structure...................................37 Cyclic Voltammetry....................................................................................................39 Summary.....................................................................................................................41 3 THE SELECTIVE PARTIAL ELECT ROOXIDATION OF METHANOL TO DIMETHOXYMETHANE WITH RUTH ENIUM/TIN HETEROBIMETALLIC COMPLEXES.............................................................................................................43 Introduction.................................................................................................................43 Chemistry of Tin.........................................................................................................43 Bonding in Heterobimetall ic Tin (II) Complexes...............................................44 Synthesis of Ruthenium / Tin (II) Complexes.....................................................44 Heterobimetallic Tin (II) Catalysts......................................................................45 Methanol as a Chemical Feedstock............................................................................48 Electrochemical Synthesis of Organic Molecules......................................................51 Synthesis.....................................................................................................................5 5 Synthesis of CpRu(TPPMS)2Cl ( 22 )...................................................................55 Synthesis of CpRu(TPPMS)2(SnCl3) ( 23 )...........................................................57 Synthesis of CpRu( 2-dppm)(SnCl3) ( 24 )...........................................................58 Synthesis of CpRu( 2-dppp)(SnCl3) ( 26 )............................................................59 NMR Data...................................................................................................................60 Cyclic Voltammetry....................................................................................................61 Electrochemical Oxidation of Methanol.....................................................................64 Electrochemical Oxidat ion of Wet Methanol.............................................................69 Electrochemical Oxidation of Dimethoxymethane....................................................71 Summary.....................................................................................................................71 4 CHEMICALLY MODIFIED ELECTROD ES CONTAINING IMMOBILIZED RUTHENIUM/TIN HETEROB IMETALLIC COMPLEXES...................................73 Introduction.................................................................................................................73 Nafion.......................................................................................................................73 Nafion Supported Metal Catalysts.....................................................................74 Chemically Modified Electrodes................................................................................76 Electrodes Modified with Ruthenium Complexes..............................................77 Preparation of CME.............................................................................................78 Electrodes Modified with Bimetallic Complexes................................................79 Synthesis.....................................................................................................................8 1 Synthesis of CpRu(PPh3)2(SnPh3) ( 27 )...............................................................81 Synthesis of CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ).................................................82

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vii Synthesis of CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 )........................................82 Synthesis of CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 )........................................83 Synthesis of CpRu(amphos)2Cl ( 31 )...................................................................83 Synthesis of CpRu(amphos)2(SnCl3) ( 32 )...........................................................84 NMR Data...................................................................................................................85 Homogeneous Studies................................................................................................86 Cyclic Voltammetry............................................................................................86 Electrochemical Oxidation of Methanol.............................................................90 Heterogeneous Studies................................................................................................96 Preparation of Modified Toray Ca rbon Paper (MTCP) Electrodes.....................96 Cyclic Voltammetry............................................................................................99 Summary...................................................................................................................101 5 EXPERIMENTAL PROTOCOLS...........................................................................103 General Considerations.............................................................................................103 Electrochemistry.......................................................................................................104 Electrode Fabrication.........................................................................................105 Product Analysis................................................................................................105 Preparation of Modified Electrodes...................................................................105 Synthesis...................................................................................................................106 CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 )............................................................106 CpRu(PPh3)(-Cl)(-dppm)Hg(OAc)2 ( 18 )......................................................107 CpRu(TPPMS)2Cl ( 22 )......................................................................................107 CpRu(TPPMS)2(SnCl3) ( 23 ).............................................................................107 CpRu( 2-dppm)(SnCl3) ( 24 )..............................................................................108 CpRu( 2-dppp)(SnCl3) ( 26 )...............................................................................108 CpRu(PPh3)2(SnPh3) ( 27 )..................................................................................109 CpRu(Ph2PCH2CH2N(CH3)2)2Cl ( 28 )...............................................................109 CpRu(Ph2PCH2CH2N(CH3)2)2(SnCl3) ( 29 ).......................................................110 CpRu(Ph2PCH2CH2N(CH3)2)2(SnPh3) ( 30 )......................................................110 CpRu(Ph2PCH2CH2N(CH3)3BF4)2Cl ( 31 ).........................................................111 CpRu(Ph2PCH2CH2N(CH3)3BF4)2(SnCl3) ( 32 ).................................................111 Ph2PCH2CH2N(CH3)2........................................................................................111 Ph2PCH2CH2N(CH3)3BF4..................................................................................112 [( 5-C5H4(CH2)2N(CH3)2H)Ru(-dppm)(-CO)2IrCl2]Cl.................................112 Crystallographic Structur e Determination of CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 )...............................................................113 LIST OF REFERENCES.................................................................................................115 BIOGRAPHICAL SKETCH...........................................................................................128

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viii LIST OF TABLES Table page 1-1 Catalytic oxidation of 1-phenylethanol....................................................................16 1-2 Formal potentials for complexes 3, 4, 5 and 7 .........................................................18 1-3 Bulk electrolysis data fo r the oxidation of methanol by 3 7 ..................................20 2-1 Formal potentials for complexes 8 14 ....................................................................24 2-2 Bulk electrolysis data fo r the oxidation of methanol by 8 14 ................................25 2-3 Selected NMR data for complexes 16 18 ..............................................................37 2-4 Selected bond distances () and angles (deg) for CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 )...................................................................38 2-5 Crystal data and struct ure refinement for CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 ).39 3-1 Selected ionization potentials...................................................................................44 3-2 TEMPO mediated elec trooxidation of carbohydrates..............................................53 3-3 Selected NMR data for complexes 19 – 26 ..............................................................60 3-4 Formal potentials of complexes 19 – 26 ..................................................................61 3-5 Bulk electrolysis data fo r the oxidation of methanol by 19 21 and 24 26 ...........66 3-6 Bulk electrolysis data fo r the oxidation of methanol by 22 and 23 ..........................68 3-7 Selective partial oxidation of methanol....................................................................69 3-8 Bulk electrolysis data for the oxidation of wet methanol by 20 21 and 23 .............70 4-1 Selected NMR data for complexes 27 – 32 ..............................................................85 4-2 Formal potentials of complexes 27 – 32 ..................................................................87 4-3 Bulk electrolysis data fo r the oxidation of methanol by 27 32 ..............................91

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ix 4-4 Bulk electrolysis data fo r the oxidation of methanol by 28 and 29 ..........................94 4-5 Donor number of se lected Lewis bases....................................................................96 4-6 Formal potentials for the modified electrodes MTCP-1 to MTCP-5.......................98 5-1 Formal potentials of the ferrocene/ferrocenium couple.........................................104

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x LIST OF FIGURES Figure page 1-1 Polarization data for Pt/M alloys at 60 C..................................................................6 1-2 Cyclic voltammograms of 3 .....................................................................................19 2-1 Structure of compounds 3 5 and 8 14 ..................................................................23 2-2 References to “Lewis acid” in the scientific literature.............................................27 2-3 Structure of trimeric perfluoroortho -phenylene mercury.......................................32 2-4 Unrefined crystal structure of [CpRu(PPh3)( 2-dppm)]+ [ZnCl3]( 17 )...................35 2-5 Thermal ellipsoids drawing of the molecular structure of CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 )...................................................................38 2-6 Cyclic voltammograms of 16 ...................................................................................41 3-1 Structure of compounds 19 26 ...............................................................................56 3-2 Cyclic voltammograms of 19 ...................................................................................62 3-3 Cyclic voltammograms of 20 ...................................................................................63 4-1 Structure of Nafion.................................................................................................73 4-2 Cluster-network m odel for hydrated Nafion..........................................................75 4-3 References to “chemically modified el ectrodes” in the scie ntific literature............80 4-4 Structure of compounds 27 – 32 ..............................................................................81 4-5 Cyclic voltammograms of 20 ...................................................................................88 4-6 Formation of DMM during th e electrooxidation of methanol.................................92 4-7 Formation of MF during the electrooxidation of methanol......................................92 4-8 Cyclic voltammograms of 32 ...................................................................................95

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xi 4-9 Cyclic voltammograms of MTCP-2.......................................................................100

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xii Abstract of Dissertation Pres ented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy STUDY OF HOMOGENEOUS AND HETEROGENIZED RUTHENIUM / TIN HETEROBIMETALLIC COMPLEXES: SYNTHESIS, ELECTROCHEMISTRY AND CATALYTIC PROPERTIES By Corey R. Anthony May 2006 Chair: Dr. Lisa McElwee-White Major Department: Chemistry This dissertation describes the synthesis, electrochemistry and catalytic properties of a series of Ru/Sn complexes. A singl e oxidation wave, attributed to the Ru(II/III) couple was observed in the cyclic voltamm ograms of the Ru/Sn complexes. The electrocatalytic properties of these co mplexes were investigated during the electrooxidation of methanol. The oxidati on products observed are dimethoxymethane (DMM) and methyl formate (MF). The forma tion of DMM is favored when the catalysis is performed with the Ru/Sn complexes. The selectivity of the catalysts can be tuned by varying the anodic potential. The highest cu rrent efficiency (92.4 %) and selectivity (100 %) were obtained from the electrooxid ation of methanol with CpRu(TPPMS)2(SnCl3) ( 23 ). Chemically modified electrodes were also prepared by attaching Ru/Sn complexes to the electrode surface. The electrochemical propertie s and stability of these heterogenized complexes were studi ed using cyclic voltammetry.

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xiii A novel Ru/Hg complex CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 ) was synthesized and characterized. X-ray crystallography reve aled a unique chloride and dppm linker in 16 the first time a Ru/Hg complex was isolated with these bridging moieties.

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1 CHAPTER 1 LITERATURE REVIEW Oxidation of Organic Molecules In inorganic chemistry, oxidation is clearly defined as the loss of an electron by an atom, molecule or ion accompanied with an increase in the formal oxidation state. For organic chemists the concepts of oxidation st ates and electron transfer are less easily applied, hence the definition of oxidation diffe rs slightly from inorganic to organic chemistry. Organic chemists have defined the oxidation of an organic molecule as either 1) the loss of hydrogen or 2) the replacemen t of hydrogen with a more electronegative atom such as oxygen or a halogen. The oxidation of organic mo lecules has a long history1 stemming to the 1780’s and Lavoisier’s explanation of com bustion. Observations in the 19th century linked the deterioration of many organic materials such as rubber and natural oi ls to the adsorption of dioxygen. The control of oxidation is desi rable not only for inhibiting the degradation of commercially important materials such as plastics, gasoline, and rubbers but also for promoting the selective oxidati on of hydrocarbon feedstocks su ch as olefins, alkanes and aromatic hydrocarbons. The first observation of a catalyzed oxidat ion reaction is attributed to Davy who showed in 1820 that ethanol is oxidized to acetic acid (Eq. 1.1) in the presence of CH3CH2OH + O2 CH3COOH + H2O (1.1) platinum. Since then the scope of the catal yzed oxidation reaction of organic molecules has grown tremendously, becoming basic to organic chemistry and the petrochemical [ Pt ]

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2 industry. Catalytic oxidation of ethylene to acetaldehyde (Eq. 1.2, Wacker process) was the first industrial s cale reaction that used an organopa lladium catalyst. The catalytic CH2 CH2 + H2OCH3CHO [PdCl4]2-CuCl2 (1.2) oxidation of organic molecules is now widely us ed in the synthesis of fine chemicals. These reactions are now well understood and can be utilized in synthesizing a wide array of functional groups (Scheme 1-1).2 RCH2CH CH2RCH2CH CH2 OH OH RCH2CH CH2 O RCHCH CH2 OH (H3C)3COOH + [ MoVI ] [ OsVIII ] [ SeIV ] Scheme 1-1. Adapted from reference 2. Oxidation of Alcohols The selective oxidation of alcohols to the corresponding aldehyde, ketone or carboxylic acid is of significance not only to fundamental research but also for commercial manufacturing processes. Trad itionally the oxidation of alcohols is performed with high oxidation st ate metal reagents such as chromium (VI), Mn (VI) and ruthenium (VIII). These methods have been reviewed extensively2,3 and will not be covered within this dissertation. Another ar ea of emphasis is the use of transition metal catalysts along with a chemi cal co-oxidant such as oxygen,4-9 peroxide7,8,10 or an amine

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3 N -oxide.11,12 The above transformations have al so been extensively studied and are beyond the scope of this review. One area which has recently received significant interest from the scientific community is th e electrochemical oxidation of alcohols. The literature on electrochemical ox idation of alcohols can be ro ughly grouped into two sets: heterogeneous13,14 (fuel cell) and homogeneous studies. Electrochemical Oxidation of Methanol in Fuel Cells Fuel cells have been postulated as the power generation system of the immediate future, poised to replace not only internal combustion engines15,16 but also advanced alkali16,17 batteries. Due to their simplicity, high energy efficiency and low pollution, direct methanol fuel cells (DMFCs) are esp ecially suited for use in portable electronic devices.16,17 In DMFCs aqueous methanol is el ectrochemically oxidized at the anode (Eq. 1.3) to CO2 Anodic Reaction: CH3OH + H2O CO2 + 6 H+ + 6 e(1.3) while oxygen is reduced at the cathod e (Eq. 1.4) to form water. Cathodic Reaction: 3/2 O2 + 6 H+ + 6e3 H2O (1.4) When combined, the two half reactions result in an electromotive force of 1.18 V for the overall reaction (Eq. 1.5). Overall Reaction: 3/2 O2 + CH3OH CO2 + 2 H2O E = 1.18 V (1.5) The mechanism for this oxidation has been reviewed18,19 extensively and can be summarized in two key steps: Physisorption and dehydrogenation of methanol on the electrode surface Formation of CO2 from adsorbed carbonaceous intermediates

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4 Very few electrode materials are capable of performing both reactions, and of these only platinum and platinum based electrodes ha ve displayed any encouraging activity and stability in an acidic medium. Mechanism The surface catalyzed electrooxidati on of methanol has been studied exhaustively,18,20-22 and because of this the reaction mechanism is now well understood. The mechanism was elucidated using a variety of electrochemical and spectroscopic methods. These methods include cyclic voltammetry, steady-state galvanostatic polarizations, chronoamperometry, mass spectrometry, FTIR, XAS, etc.23-25 In-situ spectroscopic experiments were very instrument al in examining adsorbed species and for identifying intermediates formed during the re action. By combining the results of cyclic voltammetry, in-situ ellipsometry, XAS, and in-situ FTIR experiments, the reaction steps below were proposed. The reac tion is thought to initially pr oceed through a series of dehydrogenation steps to adsorbed CO (Eq 1.6 1.9).18,20-22 Adsorbed CO is a widely accepted intermediate of methanol oxidation, an d its presence has been observed with the aid of various in-situ infrared spectroscopy techniques.26-28 CO and other carbonaceous intermediates can then be oxidized to carbon dioxide and desorbed from the electrode surface by reacting with adsorb ed water (Eq 1.10 1.12). The electrochemical oxidation of metha nol on Pt is a complicated reaction involving several steps; chem isorption of methanol a nd water, dehydrogenation of methanol, interaction between adsorbed CO and OH species and the formation of

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5 CO2.20,21 At potentials below 0.7 V (the potential region of interest) the rate determining step (RDS) on Pt anodes was shown to be the dissociative chemisorption of water (Eq 1.10). CH3OH + Pt (s) Pt-CH2OH + H+ + e(1.6) Pt-CH2OH + Pt (s) Pt2-CHOH + H+ + e(1.7) Pt2-CHOH + Pt (s) Pt3-CHO + H+ + e(1.8) Pt3-CHO Pt-CO + 2 Pt (s) + H+ + e(1.9) H2O + Pt (s) Pt-OH + H+ + e(1.10) Pt-CO + Pt-OH Pt-COOH (1.11a) Pt-CO + H2O Pt-COOH + H+ + e(1.11b) Pt-COOH Pt (s) + CO2 + H+ + e(1.12) Presently DMFCs are faced with a few challenging problems, foremost of which is that the overall reaction is very slow. Th e electrochemical oxidation of methanol (Eq. 1.5), though thermodynamically favored, is a kinetically sluggish reaction even at high catalyst loading. On the other hand, the electrooxidation of hydrogen (a thermodynamically similar reaction) is very fa st at low catalyst lo ading. The formation of stable intermediates (Eq. 1.6 1.9)29,30 is responsible for th e poor kinetics of the methanol oxidation reaction. Adsorbed CO in particular is strongly bound to the surface of Pt requiring a high overpot ential (approximately 0.5 V vs NHE) in order to obtain a reasonable current density. Based on these studies it is now accepted that an active surface for methanol electrooxidation must: “Activate” water at low potentials Be labile to CO chemisorption Catalyze the oxidation of CO to CO2

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6 Binary Electrocatalysts Although there has been moderate success with Pt anodes,31-33 the rapid poisoning of the surface with CO has made these elec trodes inadequate for use in DMFCs. This decision led to an intensive search for othe r materials that can improve the performance of the Pt anode during the methanol oxidati on process. Several methods have been investigated for promoting the formation of CO2 (Eq. 1.10 1.12). One method involves alloying Pt with a second metal, to a ccelerate the RDS. Since the dissociative chemisorption of water (Eq. 1.10) is the RDS, Pt was alloyed with oxophilic metals in order to increase the reaction rate. Alloys of Pt and an oxophilic metal have been investigated as electrocatalysts for over 40 ye ars. Beneficial eff ects have been observed for Pt/Sn,34,35 Pt/Ir,36 Pt/W37-40 and Pt/Ru28,41-44 electrodes. Studies of Pt alloyed with such metals shows that Ru has by far the largest catalytic effect18 (Figure 1-1). Current / mAmg-1Potential / V vsNHE 0 50100150200250 0.3 0.4 0.5 0.6 0.7 0.8 0.9Pt/Pd Pt/Au Pt Pt/Ru Pt/Os Pt/Ir Current / mAmg-1Potential / V vsNHE 0 50100150200250 0.3 0.4 0.5 0.6 0.7 0.8 0.9 Current / mAmg-1Potential / V vsNHE 0 50100150200250 0 50100150200250 0 50100150200250 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.3 0.4 0.5 0.6 0.7 0.8 0.9Pt/Pd Pt/Au Pt Pt/Ru Pt/Os Pt/Ir Figure 1-1. Polarization data for Pt/M alloys at 60 C in 2.5 M H2SO4 / 1 M CH3OH. Adapted from reference 18.

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7 Pt/Ru binary anodes Considerable effort has been expended to clarify the role of Ru in Pt/Ru binary electrodes. Of the mechanisms proposed, th e bifunctional theory has gained general acceptance.44-46 According to this mechanism, the Pt sites are responsible for the chemisorption and dehydrogenation of methanol while the Ru sites are responsible for water activation (Eq. 1.13 1.14). This is suppo rted by the fact that the discharging of water on Ru occurs at 0.2 V, while the chemisorption of methanol on Pt is favored over Ru. H2O + Ru (s) Ru-OH + H+ + 1e(1.13) Pt-CO + Ru-OH Pt (s) + Ru (s) + CO2 + H+ + 1e(1.14) In-situ CO stripping voltammetry was used to evaluate the active surface area, intrinsic catalytic effect and the surface composition of the a node. An anodic shift of the peak potential was observed for the CO stripping voltammograms of the Pt/Ru electrodes. This shift combined with the improved catalytic activity provides clear evidence that on Pt/Ru binary electrodes CO removal is th e RDS. The optimal Pt:Ru ratio is still being aggressive ly investigated, and remains a source of some controversy. At high temperatures (90 – 130 C) and on a carbon support it has b een shown that the optimal Ru content is 50 mole %.47 It is thought that at 50 % coverage the intrinsic rate constant is maximized. The alloying of Pt with non-noble metals, most notably Re48 and Mo, has been reported to result in a strong enhancement of the methanol oxidation reaction. The effectiveness of binary electrodes, esp ecially Pt/Ru, has resulted in the recent investigation of ternary Pt/Ru/Sn,49 Pt/Ru/Mo49 and Pt/Ru/W49,50 as well as quaternary systems Pt/Ru/Os/Ir,41,51,52 Pt/Ru/Mo/W53 and Pt/Ru/Sn/W.54 Only a slight to moderate

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8 improvement in activity was observed for thes e systems, relative to the Pt/Ru binary electrode. Combinatorial Screening After thirty years of research, the Pt/Ru (50/50) binary alloy remains one of the more active electrocatalysts for the metha nol oxidation reaction. This lack of a breakthrough and the high cost of the precious metals have ma de electrocatalysts a prime target for combinatorial screening. Co mbinatorial chemistry and high-throughput screening have revolutionized drug discovery and the pharmaceutical industry. These complementary technologies are now used fo r the preparation and evaluation of large numbers of formulations. Combinatorial scr eening of inorganic material has been used for almost thirty years. This method ha s been instrumental in characterizing new materials and in the development of new catalysts. Combinatorial searches for electrocat alysts by current voltage methods are extremely cumbersome, especially for la rge sample sizes. This obstacle was circumvented in 1998 by Mallouk52 who monitored the cell r eactions via a fluorescence signal. In 1999 Ward55 expanded on this method and used an automated multi-electrode array to perform the combinatorial screening. These methods have since been applied by other researchers and have led to ternary and quaternary electrode ma terials that display greater catalytic activity than Pt/Ru electrodes. Reaction Intermediates Although the complete oxidation of methanol to carbon dioxide is desired for fuel cell applications, other species are often formed l eading to a decrease in the fuel efficiency. Frequently observed by-products of metha nol oxidation include formaldehyde (Eq. 1.15)

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9 and formic acid (Eq. 1.16). These products can undergo a condensation reaction to form dimethoxymethane (DMM) (Eq. 1.17) and methyl formate (MF) (Eq. 1.18). CH3OH H2CO + 2 H+ + 2 e(1.15) H2CO HCOOH + 2 H+ + 2 e(1.16) H2CO + 2 CH3OH CH2(OCH3)2 + H2O (1.17) HCOOH + CH3OH HCOOCH3 + H2O (1.18) The current efficiency and product ratio were shown to be dependent on several variables such as temperature, anodic potential, mass transport and the catalyst type.56,57 For example when the electrolysis of methanol is performed on a smooth Pt electrode at ambient temperature the incomplete oxidation products formaldehyde and formic acid are preferred.58 However when a high surface area pl atinized Pt electrode was used the complete oxidation to carbon dioxide was favored.58 The condensation products DMM and MF were observed in the anode exhaus t of DMFCs operating at high temperatures and methanol concentration. Electrochemical Oxidation of Alcohols by Metal Complexes The electrochemical oxidation of alcohols us ing a catalyst in solution is an example of an indirect electrochemical process. It is termed indirect because it is the mediator (metal complex) not the substrate (alcohol) that is oxidized at the electrode surface (Scheme 1-2). After undergoing this activati on the mediator reacts in bulk solution with the substrate, regenerating the reduced metal complex and forming the oxidized substrate.

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10 Metal Complex (Ox) Metal Complex (Red) Substrate (Ox) Substrate (Red) Product e-Electrode Surface Bulk Solution Scheme 1-2. Adapted from reference 59. There are two means by which the mediat or can oxidize the substrate during the homogeneous reaction: 1. “Redox Catalysis”59 in which the mediator mere ly plays the role of an electron carrier (Scheme 13), transferring electrons to the substrate via an outer sphere process [ M ](red) [ M ](ox) + n e[ M ](ox) + Substrate(red) [ M ](red) + Substrate(ox) Substrate(ox) Product Scheme 1-3. 2. “Chemical Catalysis”59 in which the mediator re acts with the substrate to form an adduct (Scheme 1-4) be fore electron transfer occurs [ M ](red) [ M ](ox) + n e[ M ](ox) + Substrate(red) [ M Substrate ](ox) [ M Substrate ](ox) Product + [ M ](red) Scheme 1-4. In this dissertation only the chemical catalysis (often referred to as electrocatalysis) will be considered.

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11 Ruthenium Electrocatalysts Ruthenium polypyridyl complexes are suited as electrooxidation cataly sts due to the high stability and accessibility of multiple oxidati on states, tunable redox potentials by varying ligands and the possibility of multiple electr on transfers. The electrochemical oxidation of alcohols has been extensively studie d with ruthenium polypyridyl catalysts.60-68 Significant contribution to th is area has been made by Meyer, who in 1978 observed the 2ereduction of a Ru complex accompanie d by oxidation of triphenylphosphine to triphenylphosphine oxide (Scheme 1-5).63 The pyridine ligand how ever, is not suited to prolonged use and eventually dissociates, leadin g to an inactive oxo bridged dimer. The instability of the pyridine ligand was even tually overcome by replacing it and a bipyridine with the terpyridine (trpy) ligand.65 Of all the polypyridyl complexes investigated as electr ocatalysts, [(trpy)(bpy)RuII(OH2)]2+ has attracted the most interest. [(bpy)2pyRuIVO]2++PPh3[(bpy)2pyRuII(OPPh3)]2+[(bpy)2pyRuII(CH3CN)]2++O=PPh3 slow CH3CN fast Scheme 1-5. Adapted from reference 63. The Ru(II) aquo complex can undergo tw o reversible proton coupled 1 eoxidation steps to generate the versat ile oxidant [(trpy)(bpy)RuIV(O)]2+ (Eq. 1.19 -1.20). [ (trpy)(bpy)RuII(OH2) ]2+ [ (trpy)(bpy)RuIII(OH) ]2+ + e+ H+ (1.19) [ (trpy)(bpy)RuIII(OH) ]2+ [ (trpy)(bpy)RuIVO ]2+ + e+ H+ (1.20) As an oxidant [(trpy)(bpy)RuIV(O)]2+ is very versatile and has been used for the electrocatalytic oxidation of alkenes,69,70 ketones,68-70 aldehydes,68,71 sugars72,73 and

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12 DNA.72,74,75 A simplistic view of the catalytic cycle is shown in Scheme 1-6. In this cartoon a potential capable of oxidizing the me tal center from Ru(II) to Ru(IV) is applied at the electrode. The Ru complex is first oxi dized at the electrode surface before reacting in solution with the substrate regenerating the Ru(II) aquo complex. [ (trpy)(bpy)RuIVO ]2+[ (trpy)(bpy)RuII(OH2) ]2+Substrate (Ox) Substrate + H2O 2 H+2 e-Electrode Surface Bulk Solution Scheme 1-6. Adapted from reference 76. Since Meyer’s publication65 in 1980 on the electrocatalytic properties of [(trpy)(bpy)RuIV(O)]2+, the catalytic abilities of severa l other polypyridyl complexes have been reported. An exam ple of this is [Ru(4,4 -Me2bpy)2(PPh3)(H2O)][(ClO4)2], an active electrocatalyst that selectively oxidizes pr imary alcohols to the corresponding aldehyde.77 Cyclic voltammograms of these solutions exhibit an increase in anodic current when an alcohol is introduced. This increase in cu rrent is characteristic of the catalytic electrooxidation of alcohols by RuIV=O.78 Extensive mechanistic studies have been performed on the electrooxidation of aqueous alcoholic solutions with ruthenium co mplexes. Several mechanisms have since been proposed with each containing a Ru-oxo comp lex as the catalytically active species. The Ru-oxo bond is either generated in situ from water or is present beforehand in the

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13 pre-catalyst. The mechanisms which have been proposed are hydride transfer79,80 (Scheme 1-7), oxygen insertion81 (Scheme 1-8) and hydrogen atom abstraction82 (Scheme 1-9). RuIV=O+ HCOH CH3 CH3 COH CH3 CH3 RuO H 2+ COH+ CH3 CH3 RuIIOH+ CO CH3 CH3 RuIIOH2+ rapid + 2+ 2+ Scheme 1-7. Adapted from reference 79. [RuVI(trpy)(O)2(CH3CN)]2++ PhCH2OH C Ph OH H RuO H 2+ C Ph OH H RuIVO H 2+ (trpy)(CH3CN)(O) (trpy)(CH3CN)(O) [RuIV(trpy)(O)(CH3CN)2]2++PhCH(OH)2PhCH(OH)2PhCHO+H2O Scheme 1-8 Adapted from reference 81. RuIIIOH2++PhCHOH rapid RuIV=O2++PhCH2OH +PhCHO RuIIOH2 2+ Scheme 1-9 Adapted from reference 82. Reactivity of Bimetallic Complexes The term “catalysis” was coined by Berzeliu s in 1836 to describe a new force other than affinity that can drive a reaction to completion. The modern definition of a catalyst is any substance that accelerat es the rate of a chemical r eaction without being consumed during the reaction. From an economical and environmental standpoint, catalytic

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14 reactions currently dominate the chemical industry.83 These reactions have a considerable impact on the production of pha rmaceuticals, agrochemicals, polymers, fine chemicals, etc.84 Catalysis offers the possibility of achieving complex synthetic transformations with high efficiency, chemical and stereochemical control while minimizing, if not eliminating, waste products and solvents. Because of the distinct advantages gained from being able to catalyze chemical reactions, researchers are cons tantly trying to improve upon th e reactivity a nd selectivity of current catalysts. It is clear that the catalytic reactio ns that occur in nature are generally far superior to the reactions developed by chemis ts. The elucidation of many enzymatic processes has revealed the interact ion of two or more reactive centers during some of these catalytic transformations. The multifunctional catalysis observed in nature is rarely exploited in synthetic catalysts wh ich chiefly utilize a single reactive site. In trying to mimic the hydrolytic cl eavage of a phosphate ester bond by a metalloenzyme, Reinhoudt developed 1 a calix[4]arene functionalized with two Zn(II) metal centers. Complex 1 catalyzes the cyclization of the RNA model substrate 2-(hydroxypropyl)p -nitrophenyl phosphate85 (HPNP, Scheme 1-10) with a 23,000 fold rate increase at pH 7 and 25 C. The increased activity of 1 was explained via a bifunctional mechanism (Scheme 1-10) in which one zinc center acts as a Lewis acid and activates the phosphate group while the second activates the nucleophilic hydroxyl group. Bimetallic complexes are now an accepted means to improving the catalytic properties of some mononuclear systems.87-89 In recent years heterobimetallic complexes have also received a tremendous amount of atte ntion due to the possibility of exploiting the different reactivities of the metal centers during a chem ical reaction. An example

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15 Scheme 1-10. Adapted from reference 86. relevant to this dissertation is the Oppena uer-type oxidation of primary and secondary alcohols to the corresponding alde hyde and ketone with complex 2 (Table 1-1).90 Although the mechanism for this ca talytic cycle is not entirely clear, it is apparent that both metal fragments are crucial to the perfor mance of the catalyst. This certainty was based on the two key observations made by Severin: 1. Under similar conditions, Ru and Rh homobimetallic complexes displayed no Oppenauer-type oxidative ability (Table 1-1) 2. Ligand modification to the Ru or Rh fr agment affects the activity of the complexes Another example relevant to this dissertation is the heterobimetallic catalyst [N( n -Bu4)][M(N)R2(-O)2CrO2] where M= Ru or Os developed by Shapley.6,91 When air is used as the co-oxidant, this complex selectively oxidizes benzylic, primary and secondary alcohols at 60 C to the co rresponding carbonyl compounds. A mechanism based on the experimental results is shown in Scheme 1-11. It was proposed that after coordinating to Os there is a proton transfer to one of the bridging oxo ligands, followed

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16 by –hydride elimination and formation of th e carbonyl compound. After the carbonyl compound dissociates, molecular oxygen is ac tivated by the Os-Cr bond, regenerating the starting metal complex.6 Table 1-1. Catalytic oxidation of 1-phe nylethanol. Adapted from reference 90. OH RT, 6H 0.2 mol % catalyst 1 eq. K2CO3Acetone O <1 < 1 94Conversion / % Catalyst <1 < 1 94Conversion / % Catalyst Ru Cl Cl Cl Ph3P Ph3P O O Ph Ph Ph Ph Rh 2 O Ph Ph Ph Ph O Ph Ph Ph Ph Cl Cl Rh Rh Ru Ru Cl Cl Cl PPh3Ph3P Ph3PCl PPh3 O Heterobimetallic Elec trooxidation Catalysts Previous studies in the McElwee-White rese arch group resulted in the synthesis of three heterobimetallic complexes CpRu(PPh3)(-Cl)(-dppm)PtCl2 ( 3 ), CpRu(PPh3)(-Cl)(-dppm)PdCl2 ( 4 ) and CpRu(PPh3)(Cl)(-dppm)AuCl ( 5 ).92,93 Complexes 3 5 were prepared by reacting CpRu(PPh3)(Cl)( 1-dppm) ( 6 ) with Pt(COD)Cl2, Pd(COD)Cl2 or Au(PPh3)Cl (Scheme 1-12) at room temperature. The molecular structures of 3 5 were confirmed via X-ray crystallography and NMR.

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17 Os N R R O O Cr O O Os N R R O O Cr O O Os N R R O HO Cr O O O H P h C H2O H Os N R R O HO Cr O O O H H H O Os N R R O Cr O O H2O, PhCHO O2Os N R R O Cr O O O O Scheme 1-11. Adapted from reference 6. Ru Cl Ph2P PPh2 Ph3P Ph3P Ph2P Ru PPh2 Pt Cl Cl Cl Ph3P Ph2P Ru PPh2 Pd Cl Cl Cl Ph3P Ph2P Ru PPh2 Au Cl Cl 3 4 5 Pt(COD)Cl2Pd(COD)Cl2Au(PPh3)Cl 6 Scheme 1-12.

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18 Cyclic voltammetry (CV) of complexes 3 5 was performed in 1,2-dichloroethane (DCE) containing 0.7 M tetrabutyl ammonium trifluoromethane sulfonate (TBAT). All three complexes exhibited three oxidation wave s (Table 1-2). The first and third wave are assigned to the Ru(II/III) and Ru(III/IV) couples respectively, while the middle wave is assigned to the redox couple of the second metal. Table 1-2. Formal potentials for complexes 3, 4, 5 and 7 Complexa CoupleE1/2 (V)CoupleEpa (V)Couple Epa (V) Ru/Pt ( 3 ) RuII/III 1.21 PtII/IV 1.69 RuIII/IV 1.91 Ru/Pd ( 4 ) RuII/III 1.30 PdII/IV 1.49 RuIII/IV 1.92 Ru/Au ( 5 ) RuII/III 0.89 AuI/III 1.42 RuIII/IV 1.81 CpRu( 2-dppm)Cl ( 7 ) RuII/III 0.61 RuIII/IV 1.38 a All potentials obtained in 0.7 M TBAT / DCE and reported vs NHE. Adapted from reference 92. Cyclic voltammetry was also used in scr eening the electrocatal ytic properties of CpRu(PPh3)(-Cl)(-dppm)PtCl2 ( 3 ), CpRu(PPh3)(-Cl)(-dppm)PdCl2 ( 4 ) and CpRu(PPh3)(Cl)(-dppm)AuCl ( 5 ) towards methanol oxidation. For complex 3 the introduction of methanol (Figure 1-2) result s in a significant increase in current that coincides with the Pt(II/IV) redox wave. Th is increase in current is typical of an electrocatalytic oxidation process, and is also observed at the Pd(II/IV) redox couple of complex 4 In contrast, the catalyt ic current of the Ru/Au co mplex does not occur at the Au(I/III) couple but at the Ru(III/IV) couple. Product Formation As previously described, the surface ca talyzed electrooxidation of methanol involves a complicated multistep reaction (Eq. 1.6 – 1.12). When the electrooxidation of methanol is performed with a homogeneous catalyst, the oxidat ion products are

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19 00.51.01.52.02.5 Potential / V vsNHE0 100 200 300 400Current / A 10 mMCatalyst + 0.35 M MeOH + 5 L H2O 00.51.01.52.02.5 Potential / V vsNHE0 100 200 300 400Current / A 10 mMCatalyst + 0.35 M MeOH + 5 L H2O Figure 1-2. Cyclic voltammograms of 3 under nitrogen in 3.5 mL of DCE/0.7 M TBAT; glassy carbon working electrode; Ag/Ag+ reference electrode; 50 mV/s solutions as specified. Adapted from reference 93. formaldehyde (Eq 1.15) and formic acid (Eq 1.16 ). In the presence of excess methanol both formaldehyde and formic acid under go condensation reactions to form dimethoxymethane (Eq. 1.17) and methyl formate (Eq. 1.18) respectively. It is important to point out that with the excess of methanol present the equilibria for these reactions should favor the formation of DMM and MF. Therefore when observed, DMM is formed from the incomplete 2eoxidation of methanol. MF is formed from the 4eoxidation of methanol. Current efficiency was calculated based on the yields of DMM, MF and the total charge passed (Eq 1.21). 96485 (C mol-1) Current efficiency charge passed (C) [ 2 x DMM (mol) ] + [ 4 x MF (mol) ] x 100 (%) (1.21) =

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20 Bulk Electrolysis of Methanol The bulk electrolyses of 3 5 and the Ru model compound CpRu( 2-dppm)Cl ( 7 ) were performed at 1.7 V, the potential at which the catalytic current begins for complex 3 Oxidation with the Ru/Pd complex 4 was performed between the Pd(II/IV) and Ru(III/IV) waves, while electrol ysis with the Ru/Au compound 5 was performed between the Au(I/III) and Ru(III/IV) waves. Oxidati on of methanol with the Ru model compound 7 was performed at a potential more pos itive than the Ru(III/IV) couple. The organic products of bulk el ectrolyses of dry methanol were analyzed with a gas chromatograph (GC) and identified as di methoxymethane and methyl formate. The formation of these products is consistent w ith the electrooxidation of methanol on Pt/Ru electrodes. A result of this condensation r eaction is that water is formed during the electrolysis. Addition of water not only results in an increase in the catalytic currents for compounds 3 5 (Figure 1-2) but also favors th e formation of methyl formate (Table 1-3). Table 1-3. Bulk electrolysis data for the oxidation of methanol by 3 7 Complexa Dry Current Efficiencyb ( % ) Dry Product Ratiob(DMM / MF) Wet Current Efficiencyb ( % ) Wet Product Ratiob(DMM / MF) 3 18.6 1.20 19.5 0.41 4 24.6 0.87 20.6 0.54 5 25.4 0.46 26.1 0.34 7 3.2 7.2 0.33 a Electrolyses were performed at 1.7 V vs NHE. b Product ratio and current efficiencies after 130 C of charge passed. Adapted from reference 92. Current efficiencies for the oxidation of methanol with 3 5 and 7 are summarized in Table 1-3. Although the current efficiencies of the heterobimetallic complexes are moderate at best (18 26 %), they are still significantly highe r than that of the Ru model compound (3 7 %). These re sults indicate that there is a cooperative interaction

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21 between Ru and the second metal center resul ting in an enhancement of the catalytic properties of the heterobimetallic complexes relative to their mononuc lear components. Summary Ruthenium complexes have been studied as alcohol electrooxida tion catalysts since the 1970s. Heterobimetallic homogeneous elect rocatalysts is a fairly new field, with research being driven by the McElwee-White group. As a result of this research it is evident that the non-Ru metal center of 3 – 5 has a profound effect on the catalytic activity of the heterobimetallic complexes. The remainder of this dissertation will focus on the role of the non-Ru me tal center during th e electrooxidation of methanol with ruthenium heterobimetallic complexes.

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22 CHAPTER 2 SYNTHESIS AND ELECTROCHEMICAL PROPERTIES OF A RUTHENIUM / MERCURY HETEROBIMETALLIC COMPLEX Introduction Interest in heterobimetallic complexes has grown significantly in the last twenty years, mainly due to the potential catalyti c application of interacting metal centers.94-97 Cooperative interaction between metal centers has been shown to generate catalysts with greater reactivity and selectivity than their mononuclear components.98-100 A similar cooperative effect was observed during the el ectrooxidation of metha nol on Pt/Ru binary anodes. A cooperative effect was also obs erved during the oxidation of alcohols with Ru/Rh (Table 1-1) and Os/Cr (Scheme 1-11) homogeneous catalysts. Interest in this cooperative effect led to the synthesis, and i nvestigation of the elec trocatalytic properties of CpRu(PPh3)(-Cl)(-dppm)PtCl2 ( 3 ), CpRu(PPh3)(-Cl)(-dppm)PdCl2 ( 4 ) and CpRu(PPh3)(Cl)(-dppm)AuCl ( 5 ).92,93 Complexes 3 5 were used as catalyst during the electrooxidation of methanol a nd resulted in significantly better current efficiencies (Table 1-2) than the mononuclear model complex CpRu( 2-dppm)Cl.92 The increased activity displayed by complexes 3 5 during the methanol oxidation reaction inspired further study and led to the synthesis of 8 – 14 In complexes 8 – 14 the structures of 3 5 were altered by varying the ligands.101 The CVs of 8 14 (Table 2-1) are similar to those observed for 3 – 5 and the assignment of the redox waves were made from comparison to these complexes. Electr onic interaction between the metal centers of complexes 8 12 is observed in their CVs. The pres ence of a bridging halide promotes

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23 Ph3P Ph2P Ru PPh2 Pt Cl Cl Cl Ph3P Ph2P Ru PPh2 Pd Cl Cl Cl Ph3P Ph2P Ru PPh2 Pt I Cl Cl Ph3P Ph2P Ru PPh2 Pt I I I 3 4 8 9 Ph3P Ph2P Ru PPh2 Pd Cl Cl CH3 12 Ph3P Ph2P Ru PPh2 Pd I Cl Cl 11 Ph3P Ph2P Ru PPh2 Au Cl Cl 5 Ph3P Ph2P Ru PPh2 Pt Cl Cl CH3 10 Ph3P Ph2P Ru PPh2 Au I I 13 Ph3P Ph2P Ru PPh2 Au Cl Cl 14 4 Figure 2-1. Structure of compounds 3 5 and 8 14 this interaction, and the donation of electron density from Ru to Pd or Pt is reflected in the Ru(II/III) oxidation potential. Due to th e considerable loss of electron density, the Ru(II/III) oxidation wave for complexes 8 – 12 occurs at a much higher potential than CpRu(PPh3)(Cl)( 1-dppm) (Table 2-1). The lack of electronic interactionbetween the Ru

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24 and Au metal centers can also be observed by examining the CV data (Table 2-1). The Ru(II/III) and Au(I/III) oxidation waves of 13 and 14 are shifted only slightly relative to their monometallic model compounds. Table 2-1. Formal potentials for complexes 8 14 Complexa CoupleE1/2 (V)CoupleEpa (V) Couple Epa (V) 8 RuII/III 1.25 PtII/IV 1.54 RuIII/IV 1.90 9 RuII/III 1.10 PtII/IV 1.49 RuIII/IV 1.98 10 RuII/III 1.08 PtII/IV 1.53 RuIII/IV 1.95 11 RuII/III 1.29 PdII/IV 1.55 RuIII/IV 1.98 12 RuII/III 1.10 PdII/IV 1.50 RuIII/IV 1.95 13 RuII/III 0.89 AuI/III 1.54 RuIII/IV 1.80 14 RuII/III 0.75 AuI/III RuIII/IV 1.76 CpRu(PPh3)(Cl)( 1-dppm) ( 6 )RuII/III 0.72 CpRu(PPh3)2Cl RuII/III 0.87 a All potentials obtained in 0.7 M TBAT / DCE and reported vs NHE. Adapted from reference 101. The electrooxidation of methanol was performed with complexes 8 14 at 1.7 V in 0.7 M TBAT / DCE, forming DMM and MF (Tab le 2-2) as the only oxidation products. By expanding the Ru/M series of complexes, it is apparent that the Ru/Au complexes are less active during this re action, than the Ru/Pd and Ru/Pt co mplexes (Table 2-2). In fact the current efficiency of the Ru/Au comple xes are more comparable to the Ru model compound CpRu(PPh3)2Cl than to the Ru/Pt and Ru/Pd complexes.

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25 Role of the Non-Ru Metal Center From the current efficiencies in Table 2-2 it is evident that the non-Ru metal center is critical to the improved catalytic ability exhibited by the heterobimetallic complexes. Possible roles of the non-Ru metal include: Oxidant Activation of the Ru metal center Methanol binding site Table 2-2. Bulk electrolysis data for the oxidation of methanol by 8 14 Complexa Current Efficiency (%) Product Ratio (DMM / MF) 3b 18.6 1.20 8 43 0.98 9 39 1.26 10 32 3.02 4b 24.6 0.87 11 42 0.91 12 23 2.94 5b 25.4 0.46 13 16 2.10 14 12 2.32 CpRu(PPh3)2Cl 12 2.87 CpRu( 2-dppm)Cl 3.2 a Electrolyses performed at 1.7 V vs NHE. Pr oduct ratio and current efficiencies after 130 C of charge passed. Adapted from reference 92. b Adapted from reference 101.

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26 The oxidation of alcohols by Pt,102 Pd103-106 and Au107 complexes have literature precedent and are still bei ng actively investigated. Recent examples of these transformations with molecular oxygen as th e co-oxidant are shown in Schemes 2-1 and 2-2. Pd(OAc)2 (5.0 mol%) Pyridine (20 mol%) molecular sieves, toluene, 80 0C + H2O OH O + 1/2 O2 Scheme 2-1. Adapted from reference 105 OH O AuCl (5.0 mol%) Ligand (6.3 mol%) Toluene, 90 0C, air Conversion 100 % Yield 99 % N Ar N Ar Ligand Scheme 2-2. Adapted from reference 107. The Pt, Pd or Au center could also ac tivate the Ru by medi ating the electron density around it. The mediation of the Ru(II/III) couple of complexes 8 – 12 (Table 2-1) is an example of this. The bridging halide of complexes 8 – 12 facilitates the electronic interaction between Ru and Pt or Pd. As a resu lt of this interaction the Ru metal center of complexes 8 – 12 will be more electr ophilic than complex 6 The increased electrophilicity (Lewis acidity) of Ru would then favor the interaction / co ordination with the nucleophilic methanol substrate. The third possibility that exists is a site for methanol bindi ng. In this role the Pt, Pd or Au metal center would bind and activate th e methanol before oxidation is performed

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27 by the Ru metal center. A similar bifunctional mechanism44-46 was proposed for the oxidation of methanol by PtRu binary anodes in DMFCs. The second and third roles are closely rela ted and could possibly be performed by a Lewis acid metal center. To investigate the role of the second metal a Ru/Hg complex similar to the Ru/Pt and Ru/Pd complexes (F igure 2-1) was synthesized. Mercury was selected because it is of moderate Lewis aci dity and non-redox active within the potential window used. Lewis Acid Catalysts Lewis defined an acid in 1923 as an electr on pair acceptor while a Lewis base is an electron pair donor. The term “L ewis acid” is now used to di fferentiate this interaction from the Brnsted-Lowry acid (proton donor). Lewis acid catalyzed reactions have a rich history in organic synthesis and continue to be extensively studied (Figure 2-2). 0 200 400 600 800 1000Number of references 1975198019851990199520002005 Year Figure 2-2. References to “Lewis acid” in th e scientific literature (SciFinder Scholar).

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28 Carbon-carbon bond formation via the Friede l-Crafts reaction (Eq. 2.1), Mukaiyama aldol synthesis, the Diels-Alder and ene reac tions are classic organic reactions catalyzed by conventional Lewis acids such as AlCl3, SnCl4 or TiCl4.108 These simple Lewis acids, although very moisture sensitive, are capable of catalyzing a large number of reactions but with limited stereo-, regi oand chemoselectivity. H3C CH3 CH3 Cl + AlCl3 CH3 CH3 H3C +HCl (2.1) In this modern age of organic synthesis, se lectivity is as important a factor to the viability of a catalyst, as is its reactivity. Du e to continuing research in the field of Lewis acid catalyzed reactions, two key goals have been met. 1 The number of metals widely used in Le wis acid reagents has grown significantly. Currently more than 28 metals are used in Lewis acid catalyzed reactions each with its own attributes. The expansion of the Lewis acid reagents has led to reactivity previously unavailable to conventional Lewis acids (Eq 2.2).109 OEt O O O OEt O O O 10%Yb(OTf)312%TMEDA H2O,25C,16h + 71%(2.2)

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29 2 Design of novel ligands capable of stabil izing and promoting unique reactivity of Lewis acid metal centers. An example of this is the enantioselective Diels-Alder reaction (Eq. 2.3) reported by Kelly110 in 1986. In this reaction the C2 symmetric ligand (a derivative of binaphthol) lead s to one enantiomer being favored. OH Ph OH Ph O Ph O Ph B OH O O O O O 2 equiv 1) BH3 AcOH 2) OH O O 70 90 % yield > 98 % ee OMe H H OMe (2.3) With the use of non-traditional Lewis acids and the design of some novel ligands, the limitations of conventional Lewis acids have been to a large part surmounted. It is now possible to do Lewis acid catalyzed reactio ns under less stringent conditions, with high stereo-, regioand chemoselectivity. Classification of Lewis Acids Even though a large number of metal reagents have been used as Lewis acids during catalytic organic transformations, most of these reagents are chosen only after experimental trial and error. Trial and error is necessary because scientists currently only

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30 have a crude understanding of Le wis acidic character. There ha ve been a few attempts at classifying Lewis acidic reagents. These classi fications have been made using one of the following methods: Reactivity of a Lewis acid NMR data Theoretical calculations In 1972 Olah arranged over 130 Lewis acids based on their activity during a Friedel-Crafts reaction (Scheme 2-3).111 The Lewis acids were then placed in one of four categories: very active, moderately active, w eak or very weak (Scheme 2-3) based on the amount of products formed during the benzyl ation and subsequent isomerization. CH2Cl+ Lewis Acid Classification CH3 H2C CH3 Very active Lewis acid Isomerization Products Lewis acid Very active : High conversion, large amount of isomerization products = AlCl3, GaCl3, NbCl5, TaCl5Moderately active : High conversion, very little isomerization = InCl3, WCl6, ReCl5, SbCl5Weak : Low yield, no isomerization = SnCl4, BBr3, TiCl4, FeCl2, PtCl4Very weak : No Products = SbCl3, BeCl2, CuCl2, IrCl3, HgCl2, AuCl3 Scheme 2-3. Adapted from reference 111. Kobayashi grouped Lewis acids based on th e activity and sele ctivity during the addition reaction of a silyl enolate to an aldehyde and an aldimine (Scheme 2-4).112 Based on the experimental results the Lewis aci ds were classified as: active, weak or inactive (Scheme 2-4).

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31 Ph H O Ph H N Ph Ph Me3SiO + + MClnPh OH O Ph Ph NH O Ph Ph A B + Lewis Acid Classification Active : Yields greater than 40 % = AlCl3, GaCl3, NbCl5, TaCl5 Weak : Yields less than 40 % = FeCl2, PtCl2, RuCl3, SiCl4Inactive : No Products = HgCl, HgCl2,PdCl2, AuCl Scheme 2-4. Adapted from reference 112. Lewis Acidic Properties of Mercury Complexes In both classification schemes by Olah111 and Kobayashi112 the mercury halides HgCl and HgCl2 are listed as inactive and therefore ar e very weak Lewis acids. As with most metal complexes, the Lewis acidity of mercury is greatly affected by the ligands coordinated to it. Experiments designed at tuning the Lewis acidity through ligand variation have been performed with mercury organometallic complexes.113-116 The aim of these experiments is to investigate the mechanism by which polyfunctional Lewis acids activate carbonyl groups during or ganic reactions. It has been proposed that chelation of the carbonyl group by Lewis acids plays an im portant role in the enhanced catalytic activity. The Lewis acidity of mercury halide s can be increased by coordinating with an electron withdrawing ligand (Scheme 2-5).113 Complex 15 exhibits strong Lewis acidic character readily forming an adduct with acetone. The bidentate coordination was confirmed with a crystal struct ure of the solvent adduct.

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32 F F F F Hg Hg Cl Cl F F F F Hg Hg Cl Cl H3C CH3 O acetone15 Scheme 2-5. The Lewis acidity of the Hg metal center can be increased even more by expanding the fluorinated backbone. This strategy led to the isolation of the trimeric perfluoroortho phenylene mercury complex (Figure 2-3).115 This complex has a strong affinity for aromatic compounds and has formed isolable 1:1 adducts with bi phenyl, naphthalene, pyrene and triphenylene. The stacking of trimeric perfluoroortho -phenylene mercury and aromatic hydrocarbons result in phos phorescence being observed for the aromatic substrate. It is thought that the phosphorescence is due to a heavy atom effect of mercury promoting intersystem spin crossing from the S1 to the T1 state.115 F F F F Hg Hg F F F F F F F F Hg Figure 2-3. Structure of trimeric perfluoroortho -phenylene mercury

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33 Chemistry of Mercury Organometallic chemistry effectively starte d in 1849 when Frankland observed that metallic zinc reacts with methyl iodide. Fr ankland later extended this reaction to other metals and prepared several new orga nometallic compounds, one of which was methylmercuric iodide. Duri ng characterization of methylme rcuric iodide he recorded the nauseous taste, totally unaware of its extraordinary toxicity. Mercury compounds are extremely toxic and exposure can occur through inhalation, ingestion or dermal absorption. The amount of mercury abso rbed by the body is dependent upon the chemical form. Only 0.01 % of elemental merc ury is absorbed when ingested but methyl mercury is almost totally absorbed. In th e human body mercury accumulates in the liver, kidney, blood and brain. Due to decreased hand ling of mercury acute health effects such as cardiovascular collapse or kidney failure (b oth of which are fatal) are not as common today. Chronic health effects include central nervous system effects, kidney damage and birth defects. Genetic damage is also suspect ed. Due to the high toxicity of mercury it cannot be overstated how important it is to follow proper lab procedures when handling any material containing this element. Mercury Catalyzed Reactions There are limited examples in the literat ure for mercury catalyzed reactions. A recent example of this includes the re action between alkynes and phosphonic acid monoesters (Eq. 2.4) to yield vinyl phosphonates.117 R1C CH + R2P O OEt OH P O OEt O R1 R2 10 mol % Hg(OAc)22 mol % BF3.OEt2toluene, 80 C Yields = 50 90 % (2.4)

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34 Mercury acetate is essential to the reaction, forming the corresponding Markovnikov adducts in moderate to good yields with high regioselectivity. Little to no vinyl phosphonates were formed when other addition catalysts such as RuCl3, PdCl2(PPh3)2 and Pd(PPh3)4 were used. Another Hg(II) catalyzed reaction is th e homogeneous oxidation of methane to methanol (Eq. 2.5 – 2.8).118 This transformation is extremely selective (85 %) with high yields (43 %) in the presence of Hg(II) ions. CH4 + 2 H2SO4 CH3OSO3H + 2 H2O + SO2 (2.5) CH3OSO3H + H2O CH3OH + H2SO4 (2.6) SO2 + 1/2 O2 + H2O H2SO4 (2.7) CH4 + 1/2 O2 CH3OH (2.8) HgSO4 Synthesis and Characterization of CpRu(PPh3)(-Cl)(-dppm)HgCl2 Attempted Synthesis of CpRu(PPh3)(-Cl)(-dppm)HgCl2 (16) Initial attempts at preparing 16 involved reacting CpRu(PPh3)Cl( 1-dppm) with HgCl2. A similar method was used dur ing the synthesis of complexes 3 – 5 (Scheme 112) and for the preparation of (CO)3Ru(-Ph2PCH2NC4H8O)2HgI2 (Eq. 2.9).119 Instead of the desired dppm bridged comp lex the reaction between CpRu(PPh3)Cl( 1-dppm) ( 6 ) and HgCl2 led to the formation of [CpRu(PPh3)( 2-dppm)]+ (1 7 ) (Eq 2.10) as confirmed by 31P{1H} NMR (Table 2-3). The phosphorus NMR of 17 displayed a triplet at 50.2 ppm for the Ru bound PPh3 and a doublet at 2.2 ppm fo r the chelated dppm. ZnCl2 and CdCl2 also reacted in a similar manner and an unrefined X-ray crystal structure of the resulting Zn complex can be seen in Figure 2-4.

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35 Ru P P OC CO CO N N HgI2Ru P P OC CO CO N N HgI2 P N P NO (2.9) Ru Ph3P X Ru Ph3P + MCl2X MCl2M=Zn2+,Cd2+,Hg2+X=Cl-,I-Ph2P PPh2 Ph2P PPh2 (2.10) Figure 2-4. Unrefined crys tal structure of [CpRu(PPh3)( 2-dppm)]+ [ZnCl3]( 17 ).

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36 Synthesis of CpRu(PPh3)(-Cl)(-dppm)HgCl2 (16) An alternative route to 16 was found by first reacting CpRu(PPh3)Cl( 1-dppm) ( 6 ) with Hg(OAc)2 followed by acetyl chloride (Eq. 2.11). CpRu(PPh3)(-Cl)(dppm)HgCl2 is a yellow air and moisture stable solid. Solutions of 16 are also very stable when stored in an inert atmos phere; they however decompose upon prolonged exposed to air. The 31P{1H} NMR spectrum of complex 16 displays the expected resonances (Table 2-3). The Ru bound phosphor us signals appear as a doublet for PPh3 at 40.0 ppm (JPP = 41 Hz) and a doublet of doublets for dppm at 35.1 ppm (JPP = 41 Hz and 11 Hz). The Hg bound phosphorus appears as a doublet at 29.7 ppm (JPP = 11 Hz). Ru Ph3P Cl Hg(OAc)2CH3COCl Ph2P PPh2 Ru Ph3P Cl Ph2P PPh2 Hg Cl Cl Ru Ph3P Cl Ph2P PPh2 Hg OAc OAc 6 18 16 (2.11) Synthesis of CpRu(PPh3)(-Cl)(-dppm)Hg(OAc)2 (18) The Hg acetate intermediate CpRu(PPh3)(-Cl)(-dppm)Hg(OAc)2 ( 18 ) that is formed during the synthesis of 16 (Eq. 2.11), can be isolated cleanly and in high yields if acetyl chloride is not added to the reac tion mixture. The stability of complex 18 is very similar to 16 and it is isolated as an air and moisture stable yellow solid with moderate stability in solution. Complex 18 displays the expected 31P{1H} NMR spectrum, which is analogous to that of compound 16 (Table 2-3). The Ru bound phosphorus signals are shifted downfield relative to the analogous signals in 16 appearing as a doublet for PPh3 at 41.9 ppm (JPP = 43 Hz) and a doublet of doublets for dppm at 36.9 ppm (JPP = 43 Hz

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37 and 28 Hz). The Hg bound phosphorus signa l is shifted upfield relative to 16 appearing as a doublet at 24.1 ppm (JPP = 28 Hz). Table 2-3. Selected NMR data for complexes 16 18 Complex Ru-PPh3 Ru-dppm Hg-dppm 16 39.9 (d, JPP = 40 Hz)35.0 (dd, JPP = 40, 10 Hz)30.1 (d, JPP = 10 Hz) 17 48.0 (t, JPP = 35 Hz) 1.9 (d, JPP = 35 Hz) 18 41.9 (d, JPP = 43 Hz)36.9 (dd, JPP = 43, 28 Hz)24.1 (d, JPP = 28 Hz) Analysis of CpRu(PPh3)(-Cl)(-dppm)HgCl2 Structure Selected bond lengths and angles for 16 are shown in Table 2-4; crystallographic data and structure refinement are provided in Table 2-5. In the solid state, the crystal structure of CpRu(PPh3)(-Cl)(-dppm)HgCl2 contains the complex and two disordered DCE solvent molecules with no unusual contact s between any of these species. Complex 16 (Figure 2-5) contains a br idging chloride and dppm moie ty as do the structurally similar CpRu(PPh3)(-Cl)(-dppm)PtCl2 ( 3 ) and CpRu(PPh3)(-Cl)(-dppm)PdCl2 ( 4 ) The metal centers and bridging ligands form a distorted six-membered ring consisting of Ru, Cl3, Hg, P1, C6 and P2. The Cp ligand is bound to Ru in a 5 mode resulting in th e typical three legged piano stool conformation about the Ru cente r. The Ru-Cl bond length of 2.4577(8) in 16 is longer than distance of 2.4403(7) reported for the Ru-Cl bond in complex 4 The Ru-Cl bond in 16 is comparable to that of complex 5 [2.4598(11) ] whose chloride is not bridging. The Hg metal center is f our coordinate and forms bonds with three chlorides and a phosphorus atom to give the ex pected tetrahedral geometry. The Hg-Cl3 bond length of 2.7372(8) is shorter than the bridging chloride [2.763(9) ] reported for the Hg dimer [Hg2(Cl)2(-Cl)(-dppm)2]+ in which the Hg centers are also bridged by two dppm ligands. The bridging chloride exer ts a strong trans effect on the Hg-Cl1 bond

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38 [2.4901(11) ] making it much longer than the Hg-Cl2 bond [2.3993(9) ]. The bond lengths of both terminal chlorides are shorte r than the terminal Hg-Cl bonds reported for Rh2Cp2(-CO)(-dppm)(-HgCl2) [2.534(3) and 2.581(3) ] and within the typical range of four coordinate Hg species (2.28 – 2.68 ). Figure 2-5. Thermal ellipsoids drawi ng of the molecular structure of CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 ). Thermal ellipsoids are plotted at 50 % probability. Phenyl rings and hydrogen atoms are omitted for clarity. Table 2-4. Selected bond distan ces () and angles (deg) for CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 ). Bond Length ( ) Bond Angle ( deg ) Hg-P1 2.4143(8) P1-Hg-Cl3 90.44(2) Hg-Cl1 2.4901(11)P1-Hg-Cl1 111.24(4) Hg-Cl2 2.3993(9) Cl1-Hg-Cl3102.94(4) Hg-Cl3 2.7372(8) Cl3-Hg-Cl2104.67(3) Ru-P2 2.3193(8) Cl1-Hg-Cl2102.66(5) Ru-P3 2.3387(8) Hg-Cl3-Ru 110.87(3) Ru-Cl3 2.4577(8) P2-Ru-Cl3 92.69(3) Ru-C1 2.217(3) P3-Ru-Cl3 88.32(3) Ru-C2 2.230(3) P1-C6-P2 117.71(16) Ru-C3 2.232(3) Ru-C4 2.186(3) Ru-C5 2.178(3)

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39 Table 2-5. Crystal data and structure refinement for CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 ) Formula C52H50Cl7HgP3Ru Formula weight 1317.64 Temperature 193(2) K Wavelength 0.71073 Crystal system Monoclinic Space group Cc Unit cell dimensions a = 23.384(2) = 90 b = 11.5264(7) = 94.875(2) c = 19.295(2) = 90 Volume (3) 5182.2(6) Z 4 Density (calcd) (Mg/m3) 1.689 Absorption coefficient (mm-1) 3.739 F000 2600 Crystal size (mm3) 0.27 x 0.23 x 0.20 range (deg) 1.75 to 27.50 Index ranges -30 h 29, -14 k 14, -25 l 25 Reflections collected 22341 Independent reflections 11134[R(int) = 0.0160] Completeness to theta = 27.50 99.1 % Absorption correction Analytical Max. and min. transmission 0.5328 and 0.3680 Refinement method Full matrix least squares on F2 Data / restraints / parameters 11134 / 2 / 581 Goodness-of-fit on F2 1.023 Final R indices [I >2sigma(I)] aR1 = 0.0207 bwR2 = 0.0523 [10968] R indices (all data) aR1 = 0.0211 bwR2 = 0.526 Absolute structure parameter -0.0063(17) Largest diff. peak and hole (e.3)0.893 and -0.607 aR1 = (||Fo| |Fc||) / |Fo|, bwR2 = [ [w(Fo2 Fc2)2] / w[ Fo] 2]1/2, S = [ [w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[ 2(Fo2)+( 0.027*p)2+8.56*p], p = [max(Fo2,0)+ 2* Fc2]/3 Cyclic Voltammetry The first three ionization potential s for mercury are 10.43, 18.65 and 34.4 eV respectively. The large difference between the second and third ionization potentials is one reason why the formation of Hg(III) species is so difficult if not impossible to attain. There is only one report of a Hg(III) species, a short lived [Hg(cyclam)]3+ which was electrochemically genera ted and observed in 1976.120 Unfortunately, this experiment has

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40 never been independently confirmed. Base d on this and the absence of any oxidation waves for the model compound HgCl2(PPh3)2 (0 – 2.0 V), it was assumed that Hg(II) is non-redox active within the potential wi ndow used for these studies. During the CV studies of complex 16 three irreversible redox waves at 0.70, 1.02 and 1.50 V were observed (Figure 2-6). Three oxidation waves were unexpected since the only redox active species in the solution is the Ru(II) metal center. During previous studies on complexes 3 – 14 (Table 1-1 and Table 21) only two Ru based redox processes, the Ru(II/III) and Ru(III/IV) oxidati on waves were observed. Since Hg(II) is not redox active within the potential window us ed in these experiments there should only be two oxidation processes. With subsequent scans the first and third wave diminish in intensity, until only the second oxidation wave now shifted to 1.14 V (Figure 2-6) was observed. Analysis of the resulting soluti on after the CV experiments confirmed that CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 ) had decomposed during the CV experiments. The decomposition of 16 resulted in the formation of [CpRu(PPh3)( 2-dppm)]+ ( 17 ). A comparison of the CVs for [CpRu(PPh3)( 2-dppm)]+[PF6]and 16 after decomposition allowed the assignment of the oxidation wave at 1.14 V (Figure 2-6) to the Ru(II/III) couple of [CpRu(PPh3)( 2-dppm)]+. The first oxidation wave at 0.70 V is much lower than any observed for the halide bridged complexes 8 12 (Table 2-1). The oxidation wave at 0.70 V is instead closer to the Ru(II/III) couple of CpRu(PPh3)(Cl)( 1-dppm) ( 6 ) and CpRu(PPh3)(Cl)( -dppb)AuCl ( 14 ) (Table 2-1), complexes containing no halide bridge. The stability of 16 in 0.7 M TBAT / DCE was monitored via 31P{1H} NMR. Complete decomposition to 17 occurred after only 5 hours, without the passage of any current. A similar result was observed at lower electrolyte concentration

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41 -20 0 20 40 60 80 100 120 140 0.00.20.40.60.81.01.21.41.61.82.02.2Potential / V vs. NHECurrent / A Initial ScanRu Ph3P Cl Ph2P PPh2 Hg Cl Cl After Decomposition Ru Ph3P +Ph2P PPh2 Figure 2-6. Cyclic voltammograms of 16 under nitrogen in 3 .5 mL of DCE / 0.7 M TBAT; glassy carbon working electrode; Ag/Ag+ reference electrode; 50 mV/s scan rate. (0.1 M TBAT / DCE). The supporting electr olyte was also changed to the weakly coordinating electrolyte tetr a-n-butylammonium tetrakis (pentafluorophenyl)borate. Changing the supporting electrol yte had no effect, and CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 ) still decomposed to [CpRu(PPh3)( 2-dppm)]+ ( 17 ). These results indicate that the decomposition is not only due to the passage of current but also to the interaction of the supporting electrolyte with the complex. Summary A novel Ru/Hg complex CpRu(PPh3)(-Cl)(-dppm)HgCl2 ( 16 ) was synthesized and characterized. The metal centers are c onnected with a bridgi ng chloride and dppm

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42 ligands. This is the first reported Ru /Hg complex bridged in this manner. CpRu(PPh3)(-Cl)(-dppm)HgCl2 is unstable in solutions containing electrolyte, and rapidly decomposes to [CpRu(PPh3)( 2-dppm)]+ ( 17 ) during cyclic voltammetry. Due to the instability of 16 during the CV experiments, th e electrocatalytic properties of CpRu(PPh3)(-Cl)(-dppm)HgCl2 were not studied

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43 CHAPTER 3 THE SELECTIVE PARTIAL ELECT ROOXIDATION OF METHANOL TO DIMETHOXYMETHANE WITH RUTH ENIUM/TIN HETEROBIMETALLIC COMPLEXES Introduction The cooperative interaction between Ru/Pt, Ru/Pd and Ru/Au complexes has been shown to improve the catalytic ability of th e heterobimetallic complexes relative to the monometallic components.92,121 As mentioned before one possible role of the non-Ru metal center could be as a Lewis acid. To c ontinue the study of this interaction, a series of Ru/Sn complexes was synthe sized and characterized. Chemistry of Tin As a group 14 element, tin has the ability to form stable and relatively strong bonds with most elements in the periodic table.122 Except for the bonds formed to the heavier alkali and alkaline earth metals, most of the bonds formed to tin are covalent in character. The first and second ionization potentials for tin are similar to those of elements that readily form divalent cations (T able 3-1). Hence it is not su rprising that tin is able to form stable Sn(II) compounds. The more stable oxidation state is Sn(IV), but the energy difference between it and Sn(II) is very small (Eq 3.1). Due to the stability of the two Sn2+ Sn4+ + 2 eEo = 0.1364 V (3.1) oxidation states, there are extensive and varied chemistries for both states. Kinetically stable trivalent complexes have been isolated but generally Sn(III) is considered unstable and is thought to read ily disproportionate.

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44 Table 3-1. Selected ionization potentials Ionization Potential (eV) Element 1st 2nd 3rd 4th C 11.26024.38347.88764.492 Sn 7.344 14.63230.50240.734 Mg 7.464 15.035 Ca 6.113 11.871 Mn 7.435 15.640 Fe 7.870 16.18 Bonding in Heterobimetallic Tin (II) Complexes Tin is known to form heterobimetallic complexes containing metal-metal bonds to transition metals, lanthanides, actinides a nd group 12 metals. In bonding to transition metals, stannylenes donate two of the availa ble p electrons to the transition metal. Stannylenes can also act as Le wis acids, forming adducts with both hard and soft Lewis bases. These adducts are better Lewi s bases than the stannylenes (eg. SnCl3 is a better Lewis base than SnCl2). There are empty low lying p and d orbitals on tin, which when hybridized are capable of accepting electron dens ity from the transition metal. Due to these factors the bonds between tin a nd a transition metal contain both and components. Synthesis of Ruthenium / Tin (II) Complexes There are several synthetic r outes available for the preparation of M-Sn complexes, such as salt elimination, elimin ation of small molecules, oxid ative addition, insertion of tin (II) and transmetalation. For the group VIII metals (Fe, Ru and Os), the synthesis is often accomplished via the following methods: Salt elimination:123 Na2Ru(CO)4 + 2 Ph3SnCl (Ph3Sn)2Ru(CO)4 + 2 NaCl (3.2) Oxidative addition:124 Fe(CO)4(PPh3) + SnCl4 (SnCl3)Fe(CO)3(PPh3)Cl + CO (3.3) Insertion of SnCl2:125 CpRu(PPh3)2Cl + SnCl2 CpRu(PPh3)2(SnCl3) (3.4)

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45 Mechanistic information on the formation of M-Sn complexes is limited. The insertion of tin (II) halides however, has b een the subject of much discussion. Though not proven conclusively, there is evidence for the mechanism in Scheme 3-1. It has been proposed that the tin (II) halide first coordi nates to the halide lig and of the transition metal before rearranging intramolecularly to the three centered intermediate. LnM Y + SnX2 LnM Y SnX2 M Y SnX2 LnM SnX2Y LnM Y SnX2 Scheme 3-1. Adapted from reference 126. Evidence to support this mechanism includes th e isolation of a bridging halide complex Ir(-Cl)(SnCl2)(CO)(PPh3)2.127 The reaction between CpRu[Ph2PCH(CH3)CH2PPh2]Cl and SnCl2 (Scheme 3-2) also provides evidence for the intramolecular rearrangement, since the reaction proceeds with re tention of configuration at Ru.128 The diastereomers formed during the reaction are configurationa lly stable and therefore do not interconvert as a solid or in solution. Heterobimetallic Tin (II) Catalysts Stannylene complexes are often utilized as ca talysts or co-catalys ts due to the two following properties: 1. As a ligand, tin exerts a strong trans effect hence facilitating th e establishment of a vacant coordination site on the transition metal. 2. Tin (II) compounds readily undergo oxidati ve addition and subsequent reductive elimination. Heterobimetallic tin complexes have been used in hydrogenation,126,129 dehydrogenation,125,126,130-132 Friedel-Crafts alkylation,133 polymerization134,135 and

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46 hydroformylation.136-138 Of relevance to this dissert ation is the ther mal dehydrogenation of methanol by Ru/Sn heterobimetallic catalysts. Ru Cp Cl P P H2C C H H3C Ph Ph Ph Ph Ru Cp SnCl3 P P H2C C H H3C Ph Ph Ph Ph SnCl2Yield > 98 %Ru Cp Cl P P H2C C H H3C Ph Ph Ph Ph SnCl2Yield = 90 %Ru Cp SnCl3 P P H2C C H H3C Ph Ph Ph Ph Scheme 3-2. Adapted from reference 128. A series of Ru/Sn heterobimetallic complexes has been investigated as catalysts for the thermal dehydrogenation of methanol.132 A comparison of [RuCl2{P(OMe)3}4], [RuCl(SnCl3){P(OMe)3}4] and [Ru(SnCl3)2{P(OMe)3}3] reveals that the SnCl3 ligand is vital to the catalytic activity. [Ru(SnCl3)2{P(OMe)3}3] is the only complex that catalyzed the conversion of methanol to acetic acid or methyl acetate (due to the esterification of acetic acid).132 The mechanism for the thermal dehydrogenati on of methanol has been studied but is not yet fully understood.125,130,132,139 Carbonylation was ruled out as a possible route to methyl acetate since isotopically labeled 13CO was not incorporated into the product. The reaction path in Scheme 3-3 was then suggested based on previously observed

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47 H2CO CH3OH LnRu LnRu H2C O O CH2 LnRu CH3O O C H slow CH3CO2H reductive elimination LnRu CH3O O C H SnXm LnRu O O C CH3 SnXm H+HCO2CH3 + LnRu + H+ Scheme 3-3. Adapted from reference 139. transformations. Dehydrogenation of methanol to formaldehyde is known to occur for Ru complexes.140 It has also been reported that H2CO can react with metals to give a methyl-formato complex which upon reductive elimination yields methyl formate.141 It is then suggested by Shinoda that methyl fo rmate (which is obser ved in the reaction mixture) is isomerized to acetic acid.139 The isomerization is thought to go through a four center interaction (Scheme 3-3) which is favor ed by the soft and hard nature of Ru(II) and Sn(II) respectively. The methyl migration step is not evident, but would be stabilized

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48 by the resulting acetate bridge. Other eviden ce to support methyl migration is that ethyl and isopropyl formates also react to form pr opionic and isobutyric ac ids (or their esters) respectively.132 The Ru/Sn complexes investigated as catalysts for the dehydrogenation of methanol include CpRuP2X where X = SnF3, SnCl3 and SnBr3 and P2 = PPh3, PPh2Me and dppe.125 These catalysts were very se lective during the dehydrogenation of methanol, forming only methyl acetate. For these catalysts Gusevskaya suggested that the Lewis acidic tin halide ligand rendered Ru more electrophilic. The increased electrophilicity of Ru will favor the –hydride interaction and subsequent elimination (Eq 3.5) proposed as the rate determining step (Scheme 3-3). Ru O SnCl3 Ru H C SnCl3 C H H H Cp Cp slow O H H (3.5) Methanol as a Chemical Feedstock Due to the ease of transportation, storage and reactivity, methanol has been utilized as a chemical feedstock in several industrial processes. Examples of these include the carbonylation of methanol to ac etic acid, a chemical reagent used in the production of polymers, aspirin and solvents. The Monsanto process,142 commercialized in 1970, is based on the use of homogeneous Rh catalysts, while the Cativa process,143 commercialized in 1996, uses Ir catalysts. Co mbined, both catalytic cycles account for approximately 80 % of the acetic acid produced worldwide.143

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49 Another industrial example is the methanol to olefin or methanol to gasoline process patented in 1975 by Mobil. In this reaction methanol is c onverted to ethylene (Scheme 3-4) or propylene over so lid acid catalysts. The light olefins can then be used to produce longer chain hydrocarbons. Because of increasing demands for light olefins as a chemical feedstock, this reacti on continues to be an industria lly interesting process. n CH3OH (CH2)n gasoline n H2O Scheme 3-4. Adapted from reference 144. The selective oxidation of methanol has also been of interest as a route to several important organic chemicals such as formaldehyde,145 methyl formate146 (MF) and dimethoxymethane147-150 (DMM). Due to the low t oxicity, good solvent power, amphiphilic nature, low viscosity, low surf ace tension and high evaporation rate DMM has many industrial applications. DMM is utilized as a solvent in the cosmetic, pharmaceutical and paint industries as well as a chain length regulator during the preparation of ion exchange re sins. Another recent application of DMM is that of an additive to diesel fuel. Current Environmental Protection Agency (EPA) regulations require a 95 % reduction in harmful emissi ons from diesel engines.151 When fully implemented in 2010 it is estimated that 2.6 million tons of smog-causing nitrogen oxide (NOx) emissions and 110,000 tons of particulate matter (PM) will be reduced each year. It is proposed that these reductions in smog and particulate matte r will have a profound effect on our quality of life. An estimated 8,300 premature deat hs, 5,500 cases of chronic bronchitis and 17,600 cases of acute bronchitis in children w ill also be prevented annually. It is also estimated that more than 360,000 asthma attacks and 386,000 cases of respiratory

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50 symptoms in asthmatic children will be avoi ded every year. In a ddition, 1.5 million lost work days, 7,100 hospital visits and 2,400 emergency room visits for asthma will be prevented.151 NOx species are generated from nitrogen and oxygen under the high pressure and temperature conditions in the engine. Diesel PM is a complex aggregate of solid and liquid material, the formation of which is not exactly understood. Currently preand post-combustion methods are being examined for reducing NOx and PM emissions. One pre-combustion method uses reformulated di esel fuels containing oxygen rich additives such as certain alcohols, este rs, glycol ethers and carbonates. DMM is one additive that has been investigated and shown to reduce PM and soot emission from diesel engines. The commercial synthesis of DMM is performed using a two-step process involving oxidation of methanol to formal dehyde followed by the condensation of the methanol/formaldehyde mixtures to yield DMM. Due to increasing demands for DMM the direct conversion of methanol147-150 to DMM has been recently investigated as a possible replacement for the two step process. Rhenium oxides147,148 and heteropolyacids with Keggin structures149,150 have been reported to cataly ze the selective oxidation of methanol vapor to DMM, typically at temper atures above 400K. Among these catalysts, SbRe2O6 147,148 has the highest selectivity for D MM, converting 6.5 % of the methanol feed at 573K with a selec tivity as high as 92.5 %. Electrooxidation of methanol typically yi elds a complex mixture of products (Scheme 3-5), with the ma jor product and selectivit y dependent upon the reaction conditions.153-156 Product distributions have been de termined in conjunction with studies on direct methanol fuel cells,22,30,153,155-160 using Pt black,153,157,158 Pt/Ru157,158 and

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51 Pt/Nafion (Pt-SPE)155,156,159 anodes. The general trend is that the absence of water and lower methanol concentrations favor formalde hyde formation, with yields of DMM rising as the concentration of methanol increases. The presence of water favors formation of MF and/or complete oxidation to CO2. CH3OH H2CO HCOOH CO2 + 2 CH3OH + CH3OH 2e-, 2H+H2O 2e-, 2H+H2C(OCH3)2 + H2O HCOOCH3 + H2O 2e-, 2H+ Scheme 3-5. Adapted from reference 152. Electrochemical Synthesis of Organic Molecules Electrochemistry is a powerful technique capable of perfor ming versatile and unique organic transformations. During electro chemical reactions, organic substrates can be activated by adding (reducing) or removing (oxidi zing) electrons. The result of this process is the generation of ra dical anions or cations. Sin ce these electrons are generated from the electrode, there is no reagent waste. Because of this elec troorganic synthesis is often considered environmentally friendly. The advantages of this technique are: The selectivity of the reaction can be influenced by the applied potential Reaction rate is influenc ed by the current density Reaction conditions are typically very mild Environmentally friendly, no need fo r chemical oxidizing or reducing agents Disadvantages associated with el ectroorganic synthesis include: Special reactors and equipment, fo rtunately most of these are now commercially available

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52 Electron transfer is a heterogeneous process, therefore electrodes with large surface area must be used so as to accelerate the reaction rate Recovery of supporting electrolyte is often difficult and can be expensive The first notable application of electroch emistry to organic synthesis was reported in 1843 by Kolbe.161 During this reaction carboxylic acid s are decarboxylated to give an acyloxy radical intermediate that rapidly di merizes to form a hydrocarbon. Yields for Kolbe type electrolysis typically range from 50 – 90 %, remarkably high for a reaction generating an alkyl radical. Since the work of Kolbe wa s published, research into electrochemical synthetic transformations has been extensively studied. As a result of these studies some interesti ng reactions have been devel oped. Selected examples are shown in Eq. 3.6 – 3.9.162 It should be pointed out th at the fluorination and reduction reactions (Eq 3.7 and 3.8) are uniq ue to electrosynthesis. Oxidation: PbO2 anode H2SO4, H2O HO H2C C C H2C OH HOOCC C COOH (3.6) Fluorination: CH3 (CH2)n SO2Cl CF3 (CF2)n SO2F HF Ni anode (3.7) Reduction: Cu cathode H2O, H2SO4NO2 NHOH rearrangement NH2 OH (3.8) Hydrogenation: N N H Pb cathode H2O, H2SO4 (3.9)

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53 Electrosynthesis of organic compounds is not limited to only laboratory scale preparations, but is also widely used for industrial applications. One example is the reduction of acrylonitrile to adiponitrile (Eq. 3.10), a chemi cal feedstock used in the synthesis of nylon. The actual reaction is ve ry complicated, involvi ng parallel pathways and competing products. The major side react ions can be limited, to yield adiponitrile selectively (90 %). 2 CH2=CHCN + 2 H2O + 2 eNC(CH2)4CN + 2 OH(3.10) Table 3-2. TEMPO mediated el ectrooxidation of carbohydrates a Electrolyses performed at 0.53 V vs SC E. Adapted from reference 163.

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54 Apart from the direct electrochemical processes described above indirect electrochemical transformations are also used during the synthesis of organic compounds. An example relevant to this dissertation is the selective oxidation of carbohydrates with 2,2,6,6-tetramethylpiperidin-1-oxy l (TEMPO) (Table 3-2).163 Secondary hydroxyl groups are in most cases inert during the el ectrolysis. This selectivity allows the oxidation of carbohydrates to the corresponding car boxylic acids in moderate to excellent yields. The catalytically active species is the nitrosonium ion formed after the oneelectron oxidation of TEMPO (Scheme 3-6). The mechanism proposed for the pH > 3 1 e-Electrode N O N O N OH N O RCH2OH RCHO RCOOH Scheme 3-6. Adapted from reference 163. electrooxidation of carbohydr ates, is the same mechanism proposed by de Nooy164 for the oxidation of alcohols under basic conditions. Th e initial step is the coordination of the alkoxy to the nitroso group. After -hydride elimination the corresponding aldehyde is formed, the hydrate of which can be furt her oxidized to the carboxylic acid.

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55 The electrochemical oxidation of organic mo lecules with TEMPO is of interest for industrial applic ations because: 1. TEMPO and its derivatives ar e cheap and easily prepared 2. TEMPO is easily recovered in quant itative yields after oxidation of polysaccharides 3. As an oxidant TEMPO is very selective 4. Reaction work up is easily performed In 2002 and 2003 the McElwee-White group repo rted that Ru/Pt, Ru/Pd and Ru/Au heterobimetallic complexes can act as catal ysts during the electrochemical oxidation of methanol.92,93,101 For these complexes the non-Ru me tal center was shown to improve the catalytic properties as compared to the mononuclear model compounds CpRu( 2-dppm)Cl and CpRu(PPh3)2Cl. Related beneficial e ffects of a Lewis acidic tin center in a thermal reaction had prev iously been reported for CpRu(PPh3)2(SnCl3) ( 20 ), which selectively oxidizes methanol to methyl acetate at elevated temperatures.125,165 In order to continue the study of Le wis acidic inter actions during the electrochemical oxidation of methanol the catalytic properties of Ru/Sn complexes 19 – 26 (Figure 3-1) were studied. This chapter also describes the selective partial oxidation of methanol to dimethoxymethane using the Ru/Sn complexes CpRu(PPh3)2(SnCl3) ( 20 ), (Ind)Ru(PPh3)2(SnCl3) ( 21 ) and CpRu(TPPMS)2(SnCl3) ( 23 ). Synthesis Synthesis of CpRu(TPPMS)2Cl (22) The literature procedure for the synthesis of CpRu(TPPMS)2Cl166 yielded a complex reaction mixture in which unr eacted triphenylphosphine monosulfonate (TPPMS) and TPPMS oxide were the only identifiable compounds. Samples of 22 were instead prepared by an alternate route involving substitution of PPh3 in CpRu(PPh3)2Cl

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56 ( 19 ) with TPPMS (Eq 3.11). The reaction of TPPMS with a slight excess of CpRu(PPh3)2Cl was performed in refluxing toluene. Complex 22 was isolated in excellent yields (90 %) as an orange moderately air stable solid. The 31P{1H} NMR spectrum of CpRu(TPPMS)2Cl is very similar to that of CpRu(PPh3)2Cl, consisting of a singlet at 40 ppm. Ru Ph3P PPh3 X Ru Ph2P PPh2 X Na+ -O3S SO3 +Na ( 19 ) X = Cl ( 20 ) X = SnCl3( 22 ) X = Cl ( 23 ) X = SnCl3Ru Ph3P PPh3 SnCl3 ( 24 ) n = 1, dppm ( 25 ) n = 2, dppe ( 26 ) n = 3, dppp n Ru Ph3P PPh3 SnCl3 ( 21 ) Figure 3-1. Structure of compounds 19 26

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57 + 1.8 TPPMS Toluene 48 hours, Reflux Ru Ph3P PPh3 Cl Ru Ph2P PPh2 Cl Na+ -O3S SO3 +Na 19 22 (3.11) Synthesis of CpRu(TPPMS)2(SnCl3) (23) The Ru/Sn complex CpRu(TPPMS)2(SnCl3) was prepared in an analogous manner to CpRu(PPh3)2(SnCl3)125 by reacting 22 with a slight excess of SnCl2 (Eq. 3.12) in ethanol. The insertion of Sn into the Ru-Cl bond is facile and the reaction is complete after one hour. The resulting bright yellow so lid is moderately stable in air and in solutions of methanol and acetonitrile, but deco mposes rapidly when dissolved in water. As expected from the NMR spectrum of CpRu(PPh3)2(SnCl3),125 the 31P{1H} NMR spectrum of CpRu(TPPMS)2(SnCl3) consists of a singlet at 46 ppm with 2JP-Sn = 422 Hz. + 1.2 SnCl2 EtOH 24 hours, RTRu Ph2P PPh2 Cl Na+ -O3S SO3 +Na Ru Ph2P PPh2 SnCl3 Na+ -O3S SO3 +Na 22 23 (3.12) Before the synthesis of CpRu(TPPMS)2Cl ( 22 ) and CpRu(TPPMS)2(SnCl3) ( 23 ) all electrochemical experiments in the McEl wee-White lab were performed in the

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58 chlorinated solvents CH2Cl2 or DCE. CH2Cl2 or DCE had to be used because of the organic nature of the ligands used in complexes 3 – 5 and 8 – 14 These solvents have a low dielectric constant, and therefore a high ohm ic resistance. Because of the resistance, a high concentration of supporting electrolyte has to be used in order to get a reasonable conductivity and electron transf er rate. In order to im prove the electron transfer properties of the reactions being studied ther e has been a concerted effort to use more polar solvents such as methanol and wate r. As a result of this CpRu(TPPMS)2Cl ( 22 ) and CpRu(TPPMS)2(SnCl3) ( 23 ) have been synthesized. A nother reason for performing the electrochemical studies in water is to be ab le to compare these catalysts to the widely studied [(trpy)(bpy)RuII(OH2)]2+. As mentioned before the aquo ligand plays a crucial role in the catalytic cycle of [(trpy)(bpy)RuII(OH2)]2+, being deprotonated (Eq. 1.19 and 1.20) to form the catalytically active oxidant [(trpy)(bpy)RuIV(O)]2+. Synthesis of CpRu( 2-dppm)(SnCl3) (24) Complex 24 was prepared in an analogous manner to CpRu( 2-dppe)(SnCl3) in high yields (85 %), by reacting CpRu( 2-dppm)Cl with SnCl2 (Eq. 3.13). The 31P{1H} NMR spectrum consists of a singlet at 8.3 ppm with tin satellites (2JP-Sn = 385 Hz). This singlet is shifted upfield by appr oximately 6 ppm relative to CpRu( 2-dppm)Cl. The 1H NMR spectrum exhibits a shift downfield for the methylene and cyclopentadienyl protons of approximately 0.3 ppm. Ru Ph2P PPh2 Cl + 1.1 SnCl2 EtOH 5 hours, Reflux Ru Ph2P PPh2 SnCl3 24 (3.13)

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59 Synthesis of CpRu( 2-dppp)(SnCl3) (26) CpRu( 2-dppp)(SnCl3) ( 26 ) was prepared in an analogous manner to CpRu( 2-dppe)(SnCl3) in high yields (85 %), by reacting CpRu( 2-dppm)Cl with SnCl2 (Eq. 3.14). The 31P{1H} NMR spectrum consists of a singlet at 33.9 ppm, shifted upfield by approximately 5 ppm relative to CpRu( 2-dppp)Cl. Complex 26 has a low solubility in the NMR solvents used; because of th is no tin satellites were observed. The 1H NMR spectrum exhibits a shift downfield of a pproximately 0.4 ppm for the cyclopentadienyl protons. A similar shift downfield was observed for CpRu( 2-dppm)(SnCl3) ( 24 ). Ru Ph2P PPh2 Cl + 1.1 SnCl2 EtOH 5 hours, Reflux 26 Ru Ph2P PPh2 SnCl3 (3.14) The Ru/Sn complexes CpRu(PPh3)2(SnCl3) ( 20 ), (Ind)Ru(PPh3)2(SnCl3) ( 21 ) and CpRu(TPPMS)2(SnCl3) ( 23 ) are coordinatively saturated. Before the methanol oxidation reaction can occur, there ha s to be ligand dissociation and methanol coordination. Phosphine dissociation has been invoked in numerous mechanisms, and it is this reason why phosphine ligands are often used in me tal catalysts. Gusevskaya proposed that phosphine dissociation is a key step during th e thermal dehydrogenation of methanol with CpRu(PPh3)2(SnCl3) ( 20 ). To probe if a vacant coordi nation site on Ru is needed, a series of Ru/Sn complexes containing th e bidentate phosphines dppm, dppe and dppp was synthesized. If phosphine dissociation occurs dur ing the catalysis the ch elate effect of the

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60 bidentate phosphines should result in a decrease in the reaction rate of 24 – 26 relative to 20 NMR Data 1H and 31P{1H} NMR spectroscopies were utilized to determine the ligand arrangement about the Ru center. Selected NMR data are presented in Table 3-3. Only one singlet is observed in the 31P{1H} NMR spectra of these complexes suggesting that the phosphine ligands are in similar chemical environments. The proton NMR spectra of the complexes exhibit characteristic peaks for the phenyl, indenyl and cyclopentadienyl groups. The electron density at the Ru meta l center can be vari ed by changing the peripheral ligands. The chemical shifts of the cyclopentadienyl protons were predictable based on the Lewis acidity of the additional ligands. When the Lewis acidity of the ligands is increased, the Ru metal center will become electron poor and the Cp protons will become deshielded. By being deshielded the Cp protons now experience more of the applied magnetic field and shift to a higher frequency. Hence for CpRu(PPh3)2(X) the Cp resonance of X = SnCl3 (4.54 ppm) > Cl (4.10 ppm) Table 3-3. Selected NMR data for complexes 19 – 26 Complexa Solvent Cp 1H NMR (ppm) 31P{1H} NMR (ppm) 2JP,Sn (Hz) CpRu(PPh3)2Cl ( 19 ) CDCl3 4.10 39.9 CpRu(PPh3)2(SnCl3) ( 20 ) CDCl3 4.54 45.2 435 (Ind)Ru(PPh3)2(SnCl3) ( 21 ) CDCl3 48.8 363 CpRu(TPPMS)2Cl ( 22 ) DMSO-d64.07 40.1 CpRu(TPPMS)2(SnCl3) ( 23 )CD3OD 4.65 46.0 422 CpRu( 2-dppm)(SnCl3) ( 24 )CDCl3 5.08 8.3 385 CpRu( 2-dppe)(SnCl3) ( 25 ) CDCl3 4.89 77.5 397 CpRu( 2-dppp)(SnCl3) ( 26 )bCDCl3 4.84 33.9 a All NMR data obtained at room temperature. b) Low solubility no 2JP-Sn satellites observed.

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61 Cyclic Voltammetry Since Sn(II) is not redox activ e within the solvent window of these experiments, it is assumed that any observed redox processes would be due to oxidation of the Ru metal center. Cyclic voltammograms of complexes 19 26 in solutions of methanol (0.50 to 1.40 V) or DCE (0.50 to 1.60 V) each display a single oxidation wave in the potential range of the experiments. This oxidation pr ocess has previously been assigned for the monometallic complexes CpRu(PPh3)2Cl167 and (Ind)Ru(PPh3)2Cl168 (Table 3-4) as the reversible one-electron oxidation of the Ru metal center. Based on this assignment the oxidation waves observed for complexes 19 26 have been assigned to the Ru(II/III) couple. Table 3-4. Formal potentials of complexes 19 – 26 Complexa Epa (V)E1/2 b (V) Ep (mV)ipa / ipc CpRu(PPh3)2Cl ( 19 ) 0.87 0.82 90 1.03 CpRu(PPh3)2(SnCl3) ( 20 ) 1.48 1.44 85 0.92 (Ind)Ru(PPh3)2(SnCl3) ( 21 ) 1.39 1.34 106 0.95 CpRu(TPPMS)2Cl ( 22 ) 0.93 0.89 104 1.06 CpRu(TPPMS)2Cl ( 22 )c 0.79 0.73 90 0.94 CpRu(TPPMS)2(SnCl3) ( 23 ) 1.58 CpRu(TPPMS)2(SnCl3) ( 23 )c1.29 CpRu( 2-dppm)(SnCl3) ( 24 )d1.54 CpRu( 2-dppe)(SnCl3) ( 25 )d 1.53 CpRu( 2-dppp)(SnCl3) ( 26 )d 1.52 CpRu(PPh3)2Cle 0.929 0.869 120 1.00 (Ind)Ru(PPh3)2Clf 0.69 66 a All potentials obtained in 0.7 M TBAT / DCE unless otherwise specified. b E1/2 reported for reversible waves. c Potential obtained in 0.1 M TBAT/MeOH. d Potential obtained in 0.7 M TBAT/CH2Cl2. e Reference 167, potential originally reported vs SCE. f Reference 168, potential originally reported vs SCE. When analyzed in DCE, the one-electron oxidation of CpRu(PPh3)2Cl (Figure 3-2) at 0.82 V and CpRu(TPPMS)2Cl at 0.89 V are chemically reversible with ipa / ipc 1 (Table 3-4). When small amounts of meth anol are added to the DCE solutions, no

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62 significant change is observed in the cyclic voltammograms of 19 and 22 at potentials less than 1.60 V. 0.50.70.91.11.31.51.7 -40 20 40 -20 0Current / APotential / V vsNHE 5 mMCpRu(PPh3)2Cl + 0.35 M MeOH + 5 LH2O0.50.70.91.11.31.51.7 0.50.70.91.11.31.51.7 -40 20 40 -20 0 -40 20 40 -20 0Current / APotential / V vsNHE 5 mMCpRu(PPh3)2Cl + 0.35 M MeOH + 5 LH2O 5 mMCpRu(PPh3)2Cl + 0.35 M MeOH + 5 LH2O 5 mMCpRu(PPh3)2Cl + 0.35 M MeOH + 5 LH2O Figure 3-2. Cyclic voltammograms of 19 under nitrogen in 3 .5 mL of DCE / 0.7 M TBAT; glassy carbon working electrode; Ag/Ag+ reference electrode; 50 mV/s scan rate, solutions as specified in figure. Adapted from reference 169. The CV of CpRu(PPh3)2(SnCl3) ( 20 ) in DCE exhibits a revers ible Ru(II/III) couple at 1.44 V (Figure 3-3). The Ru(II/III) couple is shifted by approximately 600 mV positive with respect to the correspondi ng Ru(II/III) wave of CpRu(PPh3)2Cl ( 19 ). This positive shift is consistent with the electron withdrawing SnCl3 ligand rendering the Ru in complex 20 electron-poor relative to that of complex 19 Sn(II) is not redox active within the solvent window (-0.50 – 2.5 V vs. NHE) for these experiments. In the presence of methanol, there is a significant increase in th e current that coincides with the oxidation of the Ru metal center (Figure 3-3). This effect is indicative of an el ectrocatalytic oxidation process.

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63 -40 20 60 80 40 -20 0 100 0.50.70.91.11.31.51.7Current / APotential / V vsNHE 5 mMCpRu(PPh3)2(SnCl3) + 0.35 M MeOH + 5 LH2O -40 20 60 80 40 -20 0 100 -40 20 60 80 40 -20 0 100 0.50.70.91.11.31.51.7 0.50.70.91.11.31.51.7Current / APotential / V vsNHE 5 mMCpRu(PPh3)2(SnCl3) + 0.35 M MeOH + 5 LH2O 5 mMCpRu(PPh3)2(SnCl3) + 0.35 M MeOH + 5 LH2O 5 mMCpRu(PPh3)2(SnCl3) + 0.35 M MeOH + 5 LH2O Figure 3-3. Cyclic voltammograms of 20 under nitrogen in 3 .5 mL of DCE / 0.7 M TBAT; glassy carbon working electrode; Ag/Ag+ reference electrode; 50 mV/s scan rate, solutions as specified in figure. Adapted from reference 169. The CV of 21 is very similar to that of complex 20 exhibiting a reversible Ru(II/III) couple in DCE (Table 3-4). The Ru(II/III) couple however, at 1.34 V is 100 mV negative with respect to the an alogous Ru(II/III) couple of complex 20 This shifting of the II/III couple168 is due to additional electron dens ity associated with the indenyl ligand. The current rise from electrooxidation of methanol by 21 also coincides with its Ru(II/III) redox wave, as evidenced by a increas e in the current at 1.34 V in the presence of methanol. The CV of 23 exhibits a single irreversible wa ve in DCE at 1.58 V (Table 3-4). This irreversible redox wave has been assigned to the oxida tion of the metal center from Ru(II) to Ru(III). The single irre versible Ru(II/III) wave is al so observed in methanol at 1.29 V, shifted by approximately 290 mV relative to the redox potential in DCE. Cyclic voltammetry of 23 in DCE exhibits a significant increas e in the catalytic current at the

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64 Ru(II/III) wave when methanol is introduced. A similar catalytic effect was observed for 20 and 21 Methylene chloride solutions of CpRu( 2-dppm)(SnCl3) ( 24 ), CpRu( 2-dppe)(SnCl3) ( 25 ) and CpRu( 2-dppp)(SnCl3) ( 26 ) each exhibit a single irreversible oxidation wave at 1.54, 1.53 and 1.52 V respectively. When methanol is introduced the expected catalytic current is observed at the Ru(II/III) oxidation wave. The oxidation waves for 24, 25 and 26 (Table 3-4) are only 20 mV apart. This indicates that the structurally similar complexes also have similar electr onic configuration. Electrochemical Oxidation of Methanol The cyclic voltammograms of the Ru-SnCl3 complexes all exhibit a significant current increase in the presence of methanol As mentioned before, this increase in anodic current in the presen ce of an alcohol is charac teristic of the catalytic electrooxidation of alcohols. The onset of this electrocatalytic current for the heterobimetallic complexes coincides with th e oxidation of the metal center from Ru(II) to Ru(III). A similar current increase wa s observed in the CVs of the dppm bridged complexes CpRu(PPh3)(-Cl)(-dppm)PtCl2 ( 3 ), CpRu(PPh3)(-Cl)(-dppm)PdCl2 ( 4 ) and CpRu(PPh3)(Cl)(-dppm)AuCl ( 5 ) when methanol was introduced. For complexes 3 and 4 the increase in the anodic cu rrent coincides with the ox idation of the Pt and Pd metal center. For the Ru/Au complex the onset of the catalytic current coincides with the Ru(III/IV) redox wave. In contrast to the CV s for the heterobimetallic complexes above, the CV of the Ru model compound CpRu(PPh3)2Cl ( 19 ) (Figure 3-2) exhibits no significant current increase when methanol is introduced. In order to assess the electrocat alytic ability of the Ru-SnCl3 complexes, the electrochemical oxidation of methanol was performed at 1.7 V in 0.7 M TBAT / DCE

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65 (Table 3-5). The anodic poten tial of 1.7 V was chosen durin g the catalytic studies of 3 and is the potential at which the cat alytic current begins for complex 3 For comparison purposes initial catal ytic studies of 19 – 21 and 24 – 26 were performed at 1.7 V. At 1.7 V, the Ru in all complexes studied will be in the +3 oxidation state and within the catalytic current region. Bulk electrolysis data for the ox idation of methanol with CpRu(PPh3)2Cl ( 19 ), CpRu(PPh3)2(SnCl3) ( 20 ), (Ind)Ru(PPh3)2(SnCl3) ( 21 ), CpRu( 2-dppm)(SnCl3) ( 22 ), CpRu( 2-dppe)(SnCl3) ( 23 ) and CpRu( 2-dppp)(SnCl3) ( 24 ) are presented in Table 3-5. Differences between the activit ies of the complexes can be seen in the turnover numbers, current efficiencies and product ratios. The chelating phosphines significantly inhibited the catalytic activity of the complexes. At an anodic potential of 1.7 V, CpRu( 2-dppm)(SnCl3) ( 22 ), CpRu( 2-dppe)(SnCl3) ( 23 ) and CpRu( 2-dppp)(SnCl3) ( 24 ) exhibited little to no activity for the metha nol oxidation reaction. The heterobimetallic complexes 22 – 24 are less active than the Ru model compound CpRu(PPh3)2Cl ( 19 ). The Ru model compound CpRu(PPh3)2Cl was more active, forming significantly more oxidation products. The inactivity of the complexes with bidentate phosphine suggests that a vacant coordination site on the Ru metal ce nter is critical in the oxidation reaction.

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66 Table 3-5. Bulk electrolysis data for the oxidation of methanol by 19 21 and 24 26 Complexa Anodic Potential (V) TONb Current Efficiencyc (%) DMM (10-5 moles) MF (10-5 moles) Product Ratio (DMM/MF) CpRu(PPh3)2Cl ( 19 ) 1.70 2.60 0.157.3 0.5 6.84 0.34 2.26 0.11 3.0 1.0 CpRu(PPh3)2(SnCl3) ( 20 ) 1.70 3.37 0.2013.1 0.7 8.65 0.43 3.15 0.16 2.7 1.0 (Ind)Ru(PPh3)2(SnCl3) ( 21 ) 1.70 4.69 0.2817.9 1.0 12.1 0.60 4.34 0.22 2.8 1.0 CpRu( 2-dppm)(SnCl3) ( 24 ) 1.70 0 0 0 0 CpRu( 2-dppe)(SnCl3) ( 25 ) 1.70 0.53 0.030.78 0.09 1.85 0.09 0 CpRu( 2-dppp)(SnCl3) ( 26 ) 1.70 0 0 0 0 CpRu(PPh3)2Cl ( 19 ) 1.55 1.00 0.065.6 0.2 2.69 0.13 0.81 0.04 3.3 1.0 CpRu(PPh3)2(SnCl3) ( 20 ) 1.55 3.00 0.2018.2 0.5 9.98 0.50 0.52 0.03 19.2 1.1 (Ind)Ru(PPh3)2(SnCl3) ( 21 ) 1.55 2.80 0.1816.3 0.5 9.07 0.45 0.73 0.04 12.4 1.1 a All electrolyses performed in 0.7 M TBAT / DCE with 10 mM catalyst, 0.35 M me thanol for 5 hours unless otherwise specified. b Moles of product formed per mole of catalyst. c Calculated using Eq. 1.21.

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67 For the complexes 19 – 21 with the monodentate phosphi nes the heterobimetallic complexes are more active toward methanol oxidation. CpRu(PPh3)2(SnCl3) ( 20 ) and (Ind)Ru(PPh3)2(SnCl3) ( 21 ) form greater quantities of oxidation products than the Ru model compound CpRu(PPh3)2Cl ( 19 ). The greater reactivity is also observed in the current efficiency of these comple xes during the reaction. The Ru-SnCl3 complexes have a higher current efficiency and therefore convert a la rger portion of the ch arge passed into products. To probe the effect of the anodic poten tial on the electroche mical reaction, the oxidation of methanol with CpRu(PPh3)2Cl ( 19 ), CpRu(PPh3)2(SnCl3) ( 20 ) and (Ind)Ru(PPh3)2(SnCl3) ( 21 ) was also investigated at 1.55 V (Table 3-5). At 1.55 V, the Ru metal center in all three catalysts w ill be in the Ru(III) oxidation state during the catalysis (Table 3-4). As expected, decrea sing the anodic potentia l has a profound effect on the amounts of products and the TON (Tab le 3-5). Significantly less products are formed at the lower potential when the electrolysis is performed with 19 20 and 21 All three complexes CpRu(PPh3)2Cl ( 19 ), CpRu(PPh3)2(SnCl3) ( 20 ) and (Ind)Ru(PPh3)2(SnCl3) ( 21 ) produce more DMM than MF as evidenced by the large product ratios (Table 3-5). Reducing the anodi c potential has a significant effect on the selectivity (product ratio) of the reaction when the heterobimetallic complexes are used as catalysts. For CpRu(PPh3)2(SnCl3) ( 20 ) the product ratio increases from 2.07 to 19.2 when the potential is decreased from 1.70 to 1.55 V. A similar effect is observed for (Ind)Ru(PPh3)2(SnCl3) ( 21 ); when the potential is decrea sed the product ratio is increased from 2.79 to 12.4. When the Ru model compound is used as the catalyst, the ratio of

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68 DMM:MF is independent of the anodic poten tial, remaining virtually unchanged when the potential is decreased. Bulk electrolyses of the sulfonated complexes 22 and 23 were performed in methanol as the solvent. The electrolysis in methanol was also studied at two anodic potentials. Due to the limited anodic range of methanol, the anodic potentials used during these experiments are 1.40 V and 1.25 V. Similar to the catalysis in DCE and CH2Cl2, the electrooxidation of neat methanol resulted in the formation of DMM and MF. The same trends observed during the el ectrooxidation of methanol in DCE are also observed in neat methanol (Table 3-6): DMM formation is favored over MF, by both complexes The heterobimetallic complex is much more active than the Ru model compound When CpRu(TPPMS)2(SnCl3) is used as the catalyst, lowering the anodic potential increases th e ratio of DMM:MF When the electrolysis is performed in meth anol instead of the less polar DCE or CH2Cl2, there is a significant increase in the current efficiency, amounts of products formed and TON (Table 3-6). This increase in catalytic activity has been attributed to the improved Table 3-6. Bulk electrolysis data for the oxidation of methanol by 22 and 23 Complexa Anodic Potential (V) TONb Current Efficiencyc (%) DMM (10-5 moles) MF (10-5 moles) Product Ratio (DMM/MF) CpRu(TPPMS)2Cl ( 22 ) 1.25 13.4 0.9 63.2 2.3 46.9 2.34 0 CpRu(TPPMS)2(SnCl3) ( 23 ) 1.25 33.4 2.3 89.4 5.6 117 5.85 0 CpRu(TPPMS)2Cl ( 22 ) 1.40 15.1 1.0 76.9 2.6 52.1 2.60 0.75 0.04 69.5 1.1 CpRu(TPPMS)2(SnCl3) ( 23 ) 1.40 40.0 2.6 90.1 6.7 127 6.35 13.0 0.65 9.8 1.0 a All electrolyses performed in 0.1 M TBAT / MeOH with 10mM catalyst for 5 hours. b Moles of product formed per mole of catalyst. c Calculated using Eq. 1.21.

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69 electron transfer kinetics and to the hi gher concentration of substrate. The electrooxidation of methanol with CpRu(TPPMS)2Cl ( 22 ) and CpRu(TPPMS)2(SnCl3) ( 23 ) at 1.25 V resulted in the sel ective formation of DMM. As mentioned before, the electrochemical oxidation of methanol is a complicated reaction (Scheme 3-5) that often forms multiple stable products (eg. H2CO, HCOOH, CO, H2C(OCH3)2 and HCOOCH3). To the best of my knowl edge this is the first time that the electrooxidation of methanol result ed in a single oxidation product. When compared to the high temperature synthesis of DMM (Table 3-7), the electrochemical oxidation of methanol is a promising alternative for the synthesis of DMM. Table 3-7. Selective partia l oxidation of methanol. Catalyst Reaction Conditions DMM Selectivity (%) Conversion H4PVMo11O40 / SiO2 a 493 K, 4 kPa CH3OH, 9 kPa O2 58.1 68 SbRe2O6 b 573 K, MeOH / O2 = 4.0 / 9.7 (mol %) 92.5 6.5 CpRu(TPPMS)2Cl ( 22 ) 1.25 V, 0.1 M TBAT / MeOH 100 63.2c CpRu(TPPMS)2(SnCl3) ( 23 ) 1.25 V, 0.1 M TBAT / MeOH 100 89.4c a Reference 150. b Reference 148. c Current efficiency (Eq. 1.21). Electrochemical Oxidation of Wet Methanol The CVs of the heterobimetallic complexes 20 (Figure 3-3), 21 and 23 all display a slight increase in the catal ytic current when small amount s of water are added to the reaction mixtures. It should be noted that all of the samples cont ain some water due to the condensation of methanol with formalde hyde to generate DMM (Scheme 3-5). The effect of additional water on the electrocat alytic reaction was probed by introducing 5 L of water before starting the electrolysis. In DCE the addition of water has a profound

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70 effect on the selectivity of the reaction. The product ratio for the oxidation of “wet” methanol is lower than the corresponding electr olysis in “dry” methanol (Table 3-8). The addition of water therefore favors the formati on of MF. A similar effect was previously described for heterogenous148 and similar ruthenium92,93 catalysts. Table 3-8. Bulk electrolysis data for the oxidation of wet methanol by 20 21 and 23 Complexa Anodic Potential (V) TONb Current Efficiencyc (%) DMM (10-5 moles) MF (10-5 moles) Product Ratio (DMM / MF) CpRu(PPh3)2(SnCl3) ( 20 ) 1.55 2.50 0.14 17.2 0.5 6.45 0.32 2.30 0.11 2.8 1.0 (Ind)Ru(PPh3)2(SnCl3) ( 21 ) 1.55 2.90 0.16 20.7 0.6 6.67 0.33 3.48 0.17 1.9 1.0 CpRu(TPPMS)2(SnCl3) ( 23 )d 1.25 15.3 0.9 74.2 3.1 42.1 2.10 11.5 0.57 3.7 1.0 a All electrolyses performe d in 0.7 M TBAT / DCE with 0.35 M methanol and 5.0 L H2O for 5 hours unless ot herwise specified. b Moles of product formed per mole of catalyst. c Calculated using Eq. 1.21. d Electrolyses performed in 0.1 M TBAT/MeOH with 5.0 L H2O for 5 hours. Methyl formate formation is also favored in “wet” vs “dry” methanol when the electrolysis is performed in methanol with CpRu(TPPMS)2(SnCl3) ( 23 ). There is however a significant decrease in the TON a nd current efficiency of the catalyst (Table 3-8). During the synthesis of CpRu(TPPMS)2(SnCl3), it was observed that this complex was very unstable in aqueous solutions. The decrease in TON and current efficiency is probably due to a shorter catalyst lifetime in aqueous solutions. This premise is supported by 31P{1H} NMR that revealed more TPPMS oxide in the “wet” solutions than in the “dry” solutions. CpRu(PPh3)2(SnCl3) and (Ind)Ru(PPh3)2(SnCl3) are also unstable in solutions containing water. The low solubility of water in DCE probably

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71 accounts for why no significant change in the TON and current efficiency of CpRu(PPh3)2(SnCl3) and (Ind)Ru(PPh3)2(SnCl3) was observed. Electrochemical Oxidation of Dimethoxymethane The electrooxidation of DMM was studied in order to test the competency of DMM as an intermediate on the pathway to met hyl formate. Control experiments have established that the electrooxi dation of DMM in DCE does not proceed in the absence of catalyst at a potential of 1.70 V. The CV of CpRu(PPh3)2(SnCl3) ( 20 ) exhibits no catalytic current in the presence of DMM. After 5 hours of electro lysis at 1.7 V complex 20 formed 6.64 x 10-5 moles of MF with a current effi ciency of 14.3 %. These results indicate that DMM could be an intermedia te during the oxidation of methanol to MF Summary A series of heterobimetallic comple xes containing a Ru-Sn metal bond were synthesized and characterized. The cataly tic activity of these complexes was then investigated during the electro chemical oxidation of methanol The catalytic activity of these complexes is sensitive to the ligands coordinated to ruthenium. Complexes containing a bidentate phosphine ( 24 – 26 ), display little to no catalytic activity (at an anodic potential of 1.7 V) during the electrolysis of methanol. This supports the premise that a vacant coordination site on Ru is cr itical to the electro oxidation reaction. Complexes containing a monodentate phosphine ( 19 – 23 ), catalyze the electrochemical oxidation of methanol to DMM and MF. The Ru/Sn catalysts 20 21 and 23 favor the formation of DMM; this selectiv ity can be increased by lowering the anodic potential. The electrooxidati on of methanol is more effi cient and selective for the TPPMS complexes 22 and 23 which allow the oxidation to be performed in methanol.

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72 The partial oxidation of methanol to DMM was achieved selectively (100 %) and efficiently (89.4 %) with CpRu(TPPMS)2(SnCl3) ( 23 ). The addition of water to the DCE and meth anol solutions favors the formation of MF. In methanol, the presence of water increas es the decomposition rate of the catalyst. With a shorter catalyst lifetime there is a sign ificant decrease in the current efficiency and amount of products when water is added to the methanol solutions. Due to the low solubility of water in DCE, the catalyst lifetim e is not affected by the addition of water to the DCE solutions.

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73 CHAPTER 4 CHEMICALLY MODIFIED ELECTROD ES CONTAINING IMMOBILIZED RUTHENIUM/TIN HETEROB IMETALLIC COMPLEXES Introduction Electrochemistry is a powerful and versat ile method for the synthesis of organic molecules. Transition metals are often used as catalysts / mediators to increase the reaction rates of these electrochemical reactions As with most cata lytic cycles involving transition metals, for commercial applications th ere is a desire to re cycle the catalyst. One method of achieving this is by attaching the catalyst to the electrode surface. These chemically modified electrodes (CME) have an extensive history, and excellent reviews on their application have been published.170-172 In this chapter, el ectrodes modified with cationic ruthenium complexes will be prepared and studied. Nafion Nafion is a fluorinated polymer (Figure 4-1) consisting of a fluorocarbon backbone and side chains that terminate in an anionic sulfonate site. In the commercially available membranes, the charge is typically balanced with proton or sodium ions. (CF2CF2)n CF2CF OCF2CFOCF2CF2SO3 -CF3 m Figure 4-1. Structure of Nafion where 5 n 7 and m is approximately 1000. Adapted from reference 173. Nafion was developed by DuPont in the early 1960s for use in chlor-alkali cells and was the first ionomer (synthetic polymer with ionic properties) ever synthesized.174 Other

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74 applications of Nafion include as a solid polymer electrol yte in fuel cells and batteries and a selective drying or humidi fying agent for gases. Nafion is also used as a superacid catalyst in the producti on of fine chemicals. As an ionic derivative of Teflon, Nafion has some unique properties: Mechanically stable and very resistant to chemical attack. High working temperatures, stable up to 230 C. Ion-conductive, able to function as a cation exchange resin. Super-acid catalyst, readily donating prot ons due to the stabilizing effect of the electron withdrawing fluorinated backbone on the sulfonic acid. Nafion is very selectively and highly permeable to water. The sulfonic acid groups in Nafion have a very high water of hydration, so they very efficiently absorb water. Extensive research has been perf ormed on the structure of Nafion membranes.175 As a result of this research Nafion membranes are commonly considered as segregated domains containing hydrophobic (fluorocarbon ) and hydrophilic (hydrated sulfonate) regions (Figure 4-2). When hydrated the SO3 headgroups are thought to form water containing clusters approximately 40 in diam eter. These clusters are then connected within the hydrophobic matrix by short channels 10 in diam eter. It is from this ‘inverted micelle’ structure that Nafion derives the exceptional i on selectivity and cation transport properties. Nafion Supported Metal Catalysts Because of its stability and ca tion exchange properties, Nafion has also been studied as a support for metal catalysts. S upported complexes are formed by covalently or electrostatically immobilizing metal specie s into a heterogeneous matrix. Typically the heterogeneous materials that are used as supports can be placed into three categories:

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75 1. Inorganic matrix containing surface active hydroxyl groups such as Al2O3 and SiO2 2. Organic polymers containing a pendant ligand such as polystyrene 3. Ion exchange membranes such as Nafion and polyaniline Figure 4-2. Cluster-networ k model for hydrated Nafion. Adapted from reference 176. The concept of immobilizing a soluble metal complex by attaching it to solid support was first introduced over th irty years ago. Even so this methodology still attracts considerable interest from the scientific co mmunity. The sustained interest in supported metal complexes is due to the distinct a dvantages of “heterog enized” complexes over traditional homogeneous species. Advantages of supported metal complexes include an increased reactivity and selec tivity along with recyclability, stability and an ease of separation, inherent to he terogeneous systems. As a result of the advantages listed above, supported metal complexes have been investigated for possible applications in numer ous fields. Of these applications catalysis has received the most attention, especially for the synthesis of fine chemicals. The first example of a Nafion supported metal catalyst was published in 1978 by Meidar,177 who demonstrated that a Hg impregnated Nafion membrane could catal yze the hydration of alkynes. This catalyst was easily separate d from the mixture but upon reuse there was some loss of activity.177 Since this report th ere have been several attempts at designing active Nafion supported metal species as cataly sts for organic synthesis.

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76 With properties of an excellent support, a few cationic metal complexes have been successfully immobilized onto Nafion. In several instances catalytic activities comparable to homogeneous conditions have been observed for the Nafion supported catalysts. In 1999 Seen reported the increas ed catalytic activity exhibited by a Nafion supported Pd(II) complex during th e methoxycarbonylation of ethene.178 Because this catalyst is limited by diffusion, a combination of low catalyst loading and high dispersion of Nafion was used in order to increase the activity. When this Nafion supported catalyst was used in water it was significantly more active than the unsupported catalyst, having a turnover frequency comparable to commercial applications. Chemically Modified Electrodes Chemically modified electrodes (CME) result from the modification of a conductive substrate to produce an electrode with properties that differ from that of the unmodified substrate. These electrodes ha ve been studied from the mid-1960s when French investigated the beha vior of a ferrocene modified carbon paste electrode (CPE).179 The composite nature of CPE makes these electrodes among the easiest to modify by simply admixing a third component with the graphite and binder. Other methods of preparing modified electrodes include adsorp tion, covalent attachment and coating the electrode with multi-layer films. CME are typically designed for applications such as catalysis or a sensitive sensor An excellent review on th e analytical application of sensors containing CME was published in 2003.180 Sensor applications of CME are beyond the scope of this dissertation and will not be reviewed further. Catalysis can be performed with CME if favorable conditions are present for the flow of electrons between th e electrode and the species to be oxidized or reduced.170 Scheme 4-1 shows a diagram of the reduction of A by the reduced form of the catalyst Q.

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77 The reduction can occur within the film or at the film/solution interface by means of the reaction paths shown. Electrode Surface Bulk Solution P Q P Q eA B eP Q eQ A B e-A A A A A A A Film P Q eA eB B A A A A Scheme 4-1. Adapted from reference 181. Electrodes Modified with Ruthenium Complexes CME can be used to catalyze several reactions such as CO reduction, Cr(VI) reduction, NADH oxidation, the oxidation of sma ll organic molecules such as methanol, formic acid, propene, ascorbic acid etc. These reactions were recently reviewed by Malinauskas,182 Andreev183 and Rolison.184 The first example of a ruthenium complex attached to an electrode is [(bpy)2(H2O)Ru(P4VP)n 2+] where P4VP is poly-4vinylpyridine.64 This ruthenium metallopolymer was covalently attached to the electrode surface and used as a catalyst during the elect rooxidation of isopropanol to acetone. This complex was not very stable during the cat alysis and slowly decomposed to an unidentified species.

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78 Since the CME containing a ruthenium complex was published, several other electrodes modified with rutheniu m complexes have been prepared.185-189 The methods of preparation have been varied and incl ude encapsulation of the catalyst into ionexchange membranes190-192 such as Nafion and sulfonated polystyrene. Meyer reported that the dimer [Ru(bpy)2(H2O)]2O4+ in solution is an active catalyst for the electrooxidation of water.193 When supported on polystyrene sulfonate this complex has no catalytic activity.194 Meyer proposed that the catal yst deactivation was due to the displacement of the aquo ligand and formation of a sulfonate complex. The loss of water will deactivate the catalytic reaction, by inhi biting the formation of the catalytically active oxo species. The ruthenium bound CME can also be prepar ed by attaching the metal complex to a polymer film.64,187,195,196 The stability of electrodes prepared in this manner has been studied, and is dependent on the polymer and the method of preparation. In 2000 Meyer reported that the surface bound polycis -[Ru(vbpy)2(O)2]2+ (vbpy is 4-methyl-4'-vinyl-2,2'-bipyridin e) is catalytically active dur ing the electrooxidation of alkyl and aryl alcohols.194 In solution this complex is very unstable readily losing bipyridine to form the inactive trans -dioxo complex. The rigid nature of the polymer film retards ligand loss and increases th e stability of the catalytically active cis -dioxo Ru(VI) species. Preparation of CME Typically the modified layer is assemble d upon a very stable reproducible surface. This material is normally used as an el ectrode even when unmodified due to good

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79 mechanical and chemical stability. Examples of typical materials in clude platinum, gold, tin oxide and carbon. As classified by Murray,197 CME can be grouped into four categories based on the method used to modify them: Sorption Covalently modified electrodes Polymer coatings Heterogeneous multi-layer CME prepared using sorption methods rely on ch emical and physical interactions to form and maintain the monolayer.198 These electrodes have th e advantage of being easily prepared but are not as stable as electr odes modified by other methods. Covalent modification of electrodes is another method for anchoring molecules to an electrode surface.198 Functional groups which have been employed include >C=O, >C-OH, Pt-OH and Sn-OH. As with the adsorption me thod, these electrodes are limited to monolayer coverage, severely restricting th e amount of modifier on the surface. The monolayer limitation can be overcome by preparing multi-layer CMEs. Multi-layer CME are prepared from uniform polymer coatings of ionomers, redox polymers, inorganic polymers, polymerization of me diators bearing monomers, etc.198 Another method of preparing multi-layer CME is the incorporation of mediat ors in a non-uniform matrix such as carbon paste, epoxy resin, cla y, zeolite and other polymeric systems.198 Electrodes Modified with Bimetallic Complexes CME have been aggressively studied for the la st 20 years (Figure 4-3). The modification of electrodes with bimetallic complexes however is one field that is still in its infancy, with only a handful of electrodes studied.192,199-203 The only reference to a

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80 0 500 1000 1500 2000 2500 3000Number of references 1981 19851986 19901991 19951996 20002001 2005 Year Figure 4-3. References to “chemically modified electrodes” in the scientific literature (SciFinder Scholar). heterobimetallic complex immobilized on an electrode is the Co(II)-Pt(II) porphyrin reported by Srour in 2005.204 When adsorbed to the surface of an edge plane graphite electrode a significant shift (600 mV) in the reduction pot ential of molecular oxygen was observed. This CME can act as a catalyst re ducing all of the oxygen present to water (50 %) and hydrogen peroxide (50 %). The electrochemical oxidation of methanol with Ru/Sn catalysts in solution was previously reported from this research group.169 The activity of the Ru/Sn heterobimetallic catalysts is dependent on the ancillary phosphi ne ligands. It was shown that bidentate phosphines greatly inhibited the catalytic activity of the complexes. The Ru/Sn complexes with monodentate phosphine s are very efficient (90 % current efficiency) and selective (100 % DMM) when the electrooxidation is performed in neat

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81 methanol. In order to continue the study of Ru/Sn Lewis acidic interactions, the synthesis and study of a series of Nafion supported Ru/Sn complexes (Figure 4-4) was performed. Ru L L X ( 27 ) L = PPh3, X = SnPh3( 28 ) L = Ph2PCH2CH2NMe2, X = Cl ( 29 ) L = Ph2PCH2CH2NMe2, X = SnCl3( 30 ) L = Ph2PCH2CH2NMe2, X = SnPh3( 31 ) L = Ph2PCH2CH2NMe3BF4, X = Cl ( 32 ) L = Ph2PCH2CH2NMe3BF4, X = SnCl3 Figure 4-4. Structure of compounds 27 – 32 Synthesis Synthesis of CpRu(PPh3)2(SnPh3) (27) The Ru-SnPh3 complex 27 was prepared by reacting CpRu(PPh3)2(SnCl3) ( 20 ) in benzene with an excess of phenyl lithium (Eq 4.1) at room temperature. CpRu(PPh3)2(SnPh3) was isolated as an air and moisture stable dark yellow solid in 90 % yield. Replacing the chlorides in CpRu(PPh3)2(SnCl3) with phenyl anions has a profound effect on the 31P{1H} NMR data. The singlet for the equivalent phosphorus atoms is shifted downfield relative to CpRu(PPh3)2(SnCl3) by approximately 8 ppm to 53 ppm. The P-Sn coupling is also affected ; decreasing by 165 Hz to 270 Hz. Ru Ph3P PPh3 SnCl3 + 4 PhLi Benzene 4 hours, RT Ru Ph3P PPh3 SnPh3 20 27 (4.1)

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82 Synthesis of CpRu(Ph2PCH2CH2NMe2)2Cl (28) Attempts at synthesizing complex 28 through ligand displacement from CpRu(PPh3)2Cl led to product mixtures containing the monosubstituted complex. These product mixtures were difficult to separate and therefore an alternative route to 28 was needed. Complex 28 was instead synthesi zed by reacting Ru( 2-Ph2PCH2CH2NMe2)2Cl2 with an excess of cyclopen tadiene in refluxing ethanol (Eq. 4.2). After 3 days CpRu(Ph2PCH2CH2NMe2)2Cl was isolated in high yi eld (74 %) as a yellow solid. Complex 28 is very stable as a solid or in solution even upon prolonged exposure to air and moisture. The 31P{1H} NMR spectrum of CpRu(Ph2PCH2CH2NMe2)2Cl is very similar to that of CpRu(PPh3)2Cl, consisting of a singlet at 37 ppm. Ethanol 72 hours, RefluxRu Ph2P PPh2 Cl NMe2 NMe2 P Ph2 Me2N Me2N P Ph2 Ru Cl Cl + 3 Cyclopentadiene28 (4.2) Synthesis of CpRu(Ph2PCH2CH2NMe2)2(SnCl3) (29) The reaction between CpRu(Ph2PCH2CH2NMe2)2Cl and SnCl2 in DCE (Eq 4.3) produced CpRu(Ph2PCH2CH2NMe2)2(SnCl3) in near quantitative yield. Complex 29 was isolated as a yellow solid that was stable to air and moisture not only in the solid state but also in solution. The 31P{1H} NMR spectrum is very similar to the previously synthesized Ru-SnCl3 complexes, displaying only one si nglet at 39 ppm with tin satellite couplings of 412 Hz.

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83 DCE 2 days, RTRu Ph2P PPh2 SnCl3 NMe2 NMe2 + 1.5 SnCl2Ru Ph2P PPh2 Cl NMe2 NMe2 28 29 (4.3) Synthesis of CpRu(Ph2PCH2CH2NMe2)2(SnPh3) (30) Complex 30 was prepared in a similar manner to CpRu(PPh3)2(SnPh3), by reacting CpRu(Ph2PCH2CH2NMe2)2(SnCl3) with phenyl lithium (Eq 4.4). After workup CpRu(Ph2PCH2CH2NMe2)2(SnPh3) was isolated in 64 % yield as a yellow solid. Complex 30 is stable in the presence of air and mo isture, not only as a solid but also in solution. The singlet for the equivalent phos phorus atoms is shifte d upfield relative to CpRu(PPh3)2(SnPh3) by approximately 9 ppm to 44 ppm. The P-Sn coupling (2JP-Sn = 262 Hz) of 30 is unaffected by the change in ligand environment. Toluene 4 hours, -78 CRu Ph2P PPh2 SnPh3 NMe2 NMe2 + 4 PhLi Ru Ph2P PPh2 SnCl3 NMe2 NMe2 29 30 (4.4) Synthesis of CpRu(amphos)2Cl (31) CpRu(amphos)2Cl was prepared in a similar manner to CpRu(TPPMS)2Cl, by substitution of triphenylphosphine with am phos. The ligand substitution reaction was performed in refluxing toluene (Eq. 4.5). After four days of reflux 31 was isolated in 76

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84 % yield as an orange solid. The stability of complex 31 is very similar to that of complex 28 showing no signs of decomposition even after prolonged exposure to air and moisture. The 31P{1H}NMR spectrum of 31 is very similar to that of 28 consisting of a singlet at 36 ppm. Toluene 96 hours, Reflux Ru Ph3P PPh3 Cl Ru Ph2P PPh2 Cl +NMe3 +NMe3 -BF4 -BF419 31 + 2.1 Ph2PCH2CH2NMe3BF4 (4.5) Synthesis of CpRu(amphos)2(SnCl3) (32) The Ru/Sn complex CpRu(amphos)2(SnCl3) was prepared in an analogous manner to CpRu(PPh3)2(SnCl3)125 by reacting 31 with a slight excess of SnCl2 (Eq. 4.6) in refluxing ethanol. The resulting yellow solid is stable in air and in solutions exposed to air and moisture. As expected from the NMR spectrum of CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 ), the 31P{1H} NMR spectrum of CpRu(amphos)2(SnCl3) consists of a singlet at 40 ppm with 2JP-Sn = 405 Hz. + 1.2 SnCl2 Ethanol 24 hours, RefluxRu Ph2P PPh2 SnCl3 +NMe3 +NMe3 -BF4 -BF4Ru Ph2P PPh2 Cl +NMe3 +NMe3 -BF4 -BF431 32 (4.6)

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85 As mentioned above, Nafion is a cation exchange polymer capable of acting as a solid support for positively charged species Because of this, cationic complexes analogous to CpRu(TPPMS)2Cl ( 22 ) and CpRu(TPPMS)2(SnCl3) ( 23 ) were prepared. The cationic phosphine amphos, was selected as the ligand to replace TPPMS, forming CpRu(Ph2PCH2CH2NMe3BF4)2Cl ( 31 ) and CpRu(Ph2PCH2CH2NMe3BF4)2(SnCl3) ( 32 ). The neutral complexes CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ) and CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 ) were also synthesized; these complexes will be readily protonated by Nafion to form positively charged species. NMR Data 1H and 31P{1H} NMR spectroscopies were utilized to determine the ligand arrangement about the Ru center. Selected NMR data are presented in Table 4-1. The 1H Table 4-1. Selected NMR data for complexes 27 – 32 Complexa Solvent Cp 1H NMR (ppm) 31P{1H} NMR (ppm) 2JP,Sn (Hz) CpRu(PPh3)2(SnPh3) ( 27 ) CDCl3 4.27 53.0 270 CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ) CDCl3 4.29 36.6 CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 )CDCl3 4.71 39.4 412 CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 )CDCl3 4.21 43.8 262 CpRu(amphos)2Cl ( 31 ) DMSO-d6 4.48 35.9 CpRu(amphos)2(SnCl3) ( 32 ) acetone-d65.00 39.5 405 a All NMR data obtained at room temperature. and 31P{1H} NMR spectral data are very similar to the previously reported complexes (Table 3-3). Only one si nglet is observed in the 31P{1H} NMR spectra for complexes 27 – 32 The chemical shifts of the cyclopent adienyl protons are a good indication of the electron density located on the Ru me tal center. As observed in the 1H NMR of compounds 19 – 23 (Table 3-3), the Cp protons shift downfield as the electron density on Ru decreases. Hence for CpRuL2Cl, the chemical shift of the Cp protons for

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86 L = amphos > Ph2PCH2CH2NMe2 > PPh3 TPPMS. The same trend was observed for the complexes containing the SnCl3 ligand. Homogeneous Studies Cyclic Voltammetry Cyclic voltammograms of complexes 27 32 each display a single oxidation wave (Table 4-2). This oxidation process has previo usly been assigned to the Ru(II/III) couple for the monometallic [CpRu(PPh3)2Cl,167 (Ind)Ru(PPh3)2Cl,168 CpRu(TPPMS)2Cl] and heterobimetallic [CpRu(PPh3)2(SnCl3), CpRu(TPPMS)2(SnCl3)] complexes (Table 3-3). Based on this assignment, the oxidation waves observed for complexes 27 32 have been assigned to the one-electron oxidation of Ru(II) to Ru(III). The amphiphilic nature of the amino-phosphi ne ligands allow the electrochemical study of the Ru complexes 28 32 in polar and non-polar solvents. These ligands also stabilize complexes 28 32 in water. This increased stability was observed during the characterization of these mol ecules, and during the CV st udies in aqueous solutions (Table 4-2). This contrasts to CpRu(TPPMS)2Cl ( 22 ) and CpRu(TPPMS)2(SnCl3) ( 23 ), both of which are soluble but decompose quickly in water. Due to an inductive effect, the positive charge on the amphos ligand pulls electrons density away from the Ru metal center. Because of this the Ru(II/ III) oxidation waves of complexes 31 and 32 occur at a slightly higher potential than 28 and 29 respectively. The oxidation of the Ru/Cl complex CpRu(amphos)2Cl ( 31 ) is chemically reversible (ipa / ipc 1), when analyzed in methylen e chloride, methanol, water and acetonitrile (Table 4-2). The othe r monometallic complex CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ) is also reversible when oxidized in methylene chloride methanol and water.

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87 Table 4-2. Formal potentials of complexes 27 – 32 Complexa Electrolyte Epa (V) E1/2 (V) Ep (mV) ipa / ipc CpRu(PPh3)2(SnCl3) ( 20 )b 0.7 M TBAT / DCE 1.48 1.44 85 0.92 CpRu(PPh3)2(SnCl3) ( 20 ) 0.1 M TBAT / MeNO21.42 1.35 139 1.13 CpRu(PPh3)2(SnCl3) ( 20 ) 0.1 M TBAT / CH3CN1.32, 1.50 CpRu(PPh3)2(SnPh3) ( 27 ) 0.7 M TBAT / CH2Cl21.19 1.13 116 1.21 CpRu(PPh3)2(SnPh3) ( 27 ) 0.1 M TBAT / MeOH 1.18 CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ) 0.7 M TBAT / CH2Cl21.13 1.05 134 1.04 CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ) 0.1 M TBAT / MeOH 0.97 0.90 142 1.13 CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ) 0.1 M KCl / H2O 0.86 0.80 125 1.07 CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ) 0.1 M TBAT / CH3CN0.82, 1.14 CpRu(amphos)2Cl ( 31 ) 0.7 M TBAT / CH2Cl21.18 1.12 124 1.10 CpRu(amphos)2Cl ( 31 ) 0.1 M TBAT / MeOH 1.00 0.93 114 0.99 CpRu(amphos)2Cl ( 31 ) 0.1 M TBAT / MeNO20.92 0.88 90 1.06 CpRu(amphos)2Cl ( 31 ) 0.1 M KCl / H2O 0.85 0.80 108 0.95 CpRu(amphos)2Cl ( 31 ) 0.1 M TBAT / CH3CN0.86 0.80 113 1.03 CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 )0.1 M TBAT / MeNO21.65 CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 )0.7 M TBAT / CH2Cl21.62 CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 )0.1 M TBAT / CH3CN1.52 CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 )0.1 M TBAT / MeOH 1.15 CpRu(amphos)2(SnCl3) ( 32 ) 0.1 M TBAT / MeNO21.64 CpRu(amphos)2(SnCl3) ( 32 ) 0.7 M TBAT / CH2Cl21.70 CpRu(amphos)2(SnCl3) ( 32 ) 0.1M TBAT / PC 1.73 CpRu(amphos)2(SnCl3) ( 32 ) 0.1 M TBAT / CH3CN1.59 a All potentials reported vs NHE. b Reference 169.

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88 When analyzed in acetonitrile, the CV of 28 exhibits two irreversible peaks at 0.82 and 1.14 V. The first peak at 0.82 V was assigne d to the one-electron oxidation of the Ru metal center in complex 28 This assignment was made by comparing the CV of 28 to that of 31 The second irreversible oxidation wa ve has not been conclusively assigned but is probably due to the oxida tion of an acetonitrile adduct. Figure 4-5. Cyclic voltammograms of 20 under nitrogen in 3.5 mL of CH3CN / 0.1 M TBAT; glassy carbon working electrode; Ag/Ag+ reference electrode; 50 mV/s scan rate, solutions as specified in figure. The CV of CpRu(PPh3)2(SnCl3) ( 20 ) in acetonitrile (Table 4-2) is very similar to CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ), displaying two irreversib le oxidation waves, at 1.32 and 1.50 V. At a switching potential of 1.40 V, the first oxidation wave is chemically reversible (Figure 4-5). This first oxidat ion wave has been assigned to the Ru(II/III) couple of 20 This assignment was ma de by comparing the CVs of 20 in CH3CN (Figure 4-2) to that in DCE (Figure 3-3). The second wave is irreversible, regardless of

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89 the switching potential. This oxidation process is similar to the second oxidation wave observed for 28 in CH3CN, and has been assigned to th e oxidation of an acetonitrile complex. The formation of a solvent coordinated complex has been previously reported,205 during CV studies of an an alogous ruthenium hydride complex, CpRu(PPh3)2H in acetonitrile (Eq. 4.7). CpRu(PPh3)2H 0.5 [CpRu(PPh3)2(CH3CN)]+ + 0.5 [CpRu(PPh3)2(H)2]+ CH3CN 1e(4.7) The CVs of the Ru/SnCl3 complexes CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 ) and CpRu(amphos)2(SnCl3) ( 32 ) were studied in several solv ents. A single irreversible oxidation wave was observed for 29 and 32 in MeNO2, CH2Cl2 and CH3CN. In methanol a significant increase in current was observed when 29 and 32 were added, but no oxidation waves were observed. The catalytic current of the methanol oxidation reaction obscures the Ru(II/III) redox couple. The chloride ligands in complexes CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 ) and CpRu(PPh3)2(SnCl3) ( 20 ) were substituted with the less electron withdrawing phenyl groups to yield complexes 30 and 27 A single oxidation wave, assigned to the Ru(II/III) couple was observed in the CV of complexes CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 ) and CpRu(PPh3)2(SnPh3) ( 27 ). The Ru(II/III) oxidation waves of the SnPh3 complexes 30 and 27 are shifted to lower potentials than those of the corresponding SnCl3 complexes. As predicted by Holt,126 and supported by the NMR and CV data, (SnPh3)is a weaker Lewis acid than (SnCl3)-.

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90 Electrochemical Oxidation of Methanol The cyclic voltammograms of the Ru/Sn complexes CpRu(PPh3)2(SnPh3) ( 27 ), CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 ), CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 ) and CpRu(amphos)2(SnCl3) ( 32 ) all exhibit a catalytic current in the presence of methanol. The onset of this catalytic current for the heterobimetallic complexes coincides with the oxidation of the metal center from Ru(II) to Ru(III), regardless of wh at solvent is being used. A similar current increase was obs erved in the cyclic voltammograms of CpRu(PPh3)2(SnCl3) ( 20 ) and CpRu(TPPMS)2(SnCl3) ( 23 ). For the monometallic complexes CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ) and CpRu(amphos)2Cl ( 31 ) no catalytic current was observed within the potential window (0 – 2.0 V) when methanol was introduced. The electrochemical oxidation of metha nol in 0.1 M TBAT/MeOH was performed at 1.4 V with 28 32 The anodic potential was c hosen during previous studies,169 and used for these experiments so as to have a di rect correlation to the previous results. At 1.4 V the Ru metal center of 28 30 and 31 will be oxidized from Ru(II) to Ru(III). Although no oxidation wave was observed for 29 and 32 in methanol, by extrapolating from 28 and 31 the Ru(II/III) couple for 29 and 32 can be estimated as 1.56 and 1.62 V respectively. CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 ) and CpRu(amphos)2(SnCl3) ( 32 ) are oxidized at an anodic poten tial of 1.4 V; this process ca n be observed in the CVs that display a current increase. The oxidation products formed during th e electrolysis are dimethoxymethane and methyl formate (Table 4-3). DMM and MF are the same products observed during earlier studies of Ru-TPPMS electrocatalysts169 in neat methanol. The evolution of

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91 Table 4-3. Bulk electrolysis data for the oxidation of methanol by 27 32 Complexa TONb Current Efficiencyc (%) DMM (10-5 moles) MF (10-5 moles) Product Ratio (DMM/MF) CpRu(TPPMS)2(SnCl3)d ( 23 ) 40.0 2.6 90.1 6.9 127 6 13.0 0.6 9.8 1.0 CpRu(amphos)2Cl ( 31 ) 8.85 0.6037.8 1.5 28.7 1.4 2.3 0.1 12.6 1.0 CpRu(amphos)2(SnCl3) ( 32 ) 10.3 0.6 52.1 2.1 27.9 1.4 8.2 0.4 3.4 1.0 CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ) 9.66 0.5937.7 1.9 27.2 1.4 6.6 0.3 2.5 0.6 CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 ) 10.0 0.6 47.6 2.1 24.6 1.2 10.6 0.5 2.3 1.0 CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 ) 2.14 0.148.2 0.4 7.5 0.4 N.O. CpRu(PPh3)2(SnPh3) ( 27 )e 0.80 0.064.2 0.1 2.8 0.1 N.O. CpRu(PPh3)2(SnCl3) ( 20 )d,e 3.37 0.2013.1 0.7 8.65 0.43 3.15 0.16 2.7 1.0 CpRu(PPh3)2Cl ( 19 )d,e 2.60 0.157.3 0.5 6.84 0.34 2.26 0.11 3.0 1.0 a All electrolyses performed at 1.4 V in 0.1 M TBAT/MeOH with 10 mM catalyst for 5 hours. b Moles of product formed per mole of catalyst. c Calculated using Eq. 1.21. d Reference 169. e Performed at 1.7 V in 0.7 M TBAT/CH2Cl2 with 10 mM catalyst, 0.35 M methanol for 5 hours.

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92 DMM and MF was monitored as a function of time and plotted in Figures 4-6 and 4-7 respectively. For complexes 28 29 31 and 32 DMM is formed at a faster rate than MF, Figure 4-6. Formation of DMM during the elect rooxidation of methanol at 1.4 V with Ru catalysts as specified. Figure 4-7. Formation of MF during the elect rooxidation of methanol at 1.4 V with Ru catalysts as specified.

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93 and its formation is favored all throu ghout the reaction. The Ru-aminophosphine complexes are not as active, efficient or selective as the Ru-TPPMS complexes (Table 3-5),169 forming smaller quantities of products with a lower current efficiency. After 5 hours of electrolysis with 28 29 31 and 32 oxidative currents gradually decrease to approximately 60 % of the initial value. During this time the yellow solutions developed a dark brown color. Anal ysis of the resulting solutions by 31P{1H} NMR was employed to determine what happened to the catal ysts during the electrolysis. At the end of the electrolysis, two singlets corres ponding to the major phosphorus species were observed. Based on the chemical shift, one sp ecies was identified as the oxide of the phosphine ligand. The other singlet had a chem ical shift close to the starting material, and was presumed to be a structurally sim ilar species. Similar reaction products were identified when the electrolysis was pe rformed with the TPPMS complexes. The role of tin during the catalysis is unclear. Two possibilities exist: 1. Activating the Ru metal center: Incr easing the electrophilicity of Ru was suggested by Gusevskaya (Eq. 3.5) during the thermal dehydrogenation of methanol. 2. Binding site for methanol: A similar role was invoked by Shinoda (Scheme 3-3) during the thermal dehydrogenation of methanol. Both possibilities are affected by the Lewis aci dity of the tin(II) ligand. To determine the role of tin, the phenyl substituted complexes CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 ) and CpRu(PPh3)2(SnPh3) ( 27 ) were used as catalysts during th e electrooxidation of methanol. Both complexes catalyzed the electrooxidati on of methanol, forming DMM (Table 4-3) as the only oxidation product. In neat methanol, CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 ) is a poor electrocatalyst, forming smaller quantities of products with a lower current efficiency than CpRu(Ph2PCH2CH2NMe2)2(SnCl3) ( 29 ) and

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94 CpRu(Ph2PCH2CH2NMe2)2Cl ( 28 ). A similar trend was observed when the catalytic activity of CpRu(PPh3)2(SnPh3) ( 27 ) was compared to CpRu(PPh3)2(SnCl3) ( 20 ) and CpRu(PPh3)2Cl ( 19 ) (Table 4-3). The fact that the SnPh3 complexes are less active than the SnCl3 complexes implies that the Lewis acidity of the tin(II) liga nd is an important factor in the activity of the cat alysts. The mechanistic role of tin is still unclear since decreasing its Lewis acidity influences not only the electrophilicit y of the neighboring Ru, but also the ability of tin to bind methanol. The electrochemical oxidation of methanol was also investigated in nitromethane (MeNO2), propylene carbonate (P C) and acetonitrile (CH3CN) with CpRu(amphos)2(SnCl3) ( 32 ) and CpRu(PPh3)2(SnCl3) ( 20 ). The CVs of 20 (Figure 4-5) and 32 (Figure 4-8) exhibited the anticipate d catalytic current when methanol was introduced. The potential applied during the el ectrolysis is after the Ru(II/III) oxidation wave (Table 4-4), but with in the solvent window of CH3CN, MeNO2 and PC. Although a catalytic current was observed in the CV when methanol was introduced, no oxidation products were detected during the electrolysis (Table 4-4). Table 4-4. Bulk electrolysis data for the oxidation of methanol by 28 and 29 Complexa Electrolyte Ru(II/III) Epa (V) Anodic Potential (V) TONb CpRu(PPh3)2(SnCl3) ( 20 ) 0.1 M TBAT / CH3CN1.32 1.70 0 CpRu(PPh3)2(SnCl3) ( 20 ) 0.1 M TBAT / MeNO21.42 1.70 0 CpRu(amphos)2(SnCl3) ( 32 )0.1 M TBAT / CH3CN1.59 1.80 0 CpRu(amphos)2(SnCl3) ( 32 )0.1 M TBAT / MeNO21.64 1.80 0 CpRu(amphos)2(SnCl3) ( 32 )0.1 M TBAT / PC 1.73 1.80 0 a All electrolyses performed with 10 mM catalyst and 0.35 M methanol for 5 hours. All potentials reported vs NHE. b Moles of product formed per mole of Ru complex.

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95 Figure 4-8. Cyclic voltammograms of 32 under nitrogen in 3.5 mL of PC / 0.1 M TBAT; glassy carbon working electrode; Ag/Ag+ reference electrode; 50 mV/s scan rate, solutions as specified in figure. Since CpRu(amphos)2(SnCl3) ( 32 ) and CpRu(PPh3)2(SnCl3) ( 20 ) are catalytically active in methanol and DCE, their inactivity in CH3CN, MeNO2 and PC must be as a result of the solvents. Previous results w ith chelating phosphine ligands (dppm, dppe and dppp) have established the necessity of a v acant coordination site on Ru for the reaction to proceed. The methanol oxi dation reaction is probably re tarded by the formation of solvent coordinated adducts. The formati on of solvent adducts was invoked during the CV studies of 20 and 28 in CH3CN. The ability of a solven t to coordinate to a metal center is affected by the Lewis basicity / donor number of the solvent. Donor number is a qualitative measurement of Lewis ba sicity, developed by Gutmann in 1976.206,207 Strong Lewis bases have high donor numbers, and re adily form adducts with Lewis acids. Acetonitrile and propylene carbonate are moderate Lewis bases (Table 4-5). Because of

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96 Table 4-5. Donor number of selected Lewis bases Lewis Basea Donor Number kcal. mol-1 CH2Cl2 0 DCE 0 CH3NO2 2.1 CH3CN 14.1 PC 15.1 H2O 18.0 (33.0b) CH3OH 19.0 pyridine 33.1 a Reference 206. b Bulk donor number (donor number of the Lewis base in the associated liquid) this they should readily form adducts with the Lewis acidi c metal centers of CpRu(amphos)2(SnCl3) ( 32 ) and CpRu(PPh3)2(SnCl3) ( 20 ). By comparing the donor numbers of methanol and nitromethane it is ev ident that methanol is a better Lewis base than nitromethane. It should however be not ed that these measurements were performed in dichloroethane as the solvent. A better value would be the donor number of nitromethane in nitromethane as solvent (b ulk donor number). The bulk donor number of nitromethane is expected to be grea ter than the corresponding donor number in dichlorethane, compare water in Table 4-5. It is thought that the large excess of nitromethane, acetonitrile and propylene car bonate favors the formation of solvent adducts, overcoming the thermodynamic preference if any for methanol. Heterogeneous Studies Preparation of Modified Toray Carbon Paper (MTCP) Electrodes Two methods were utilized for pr eparing the modified electrodes: Method A) The metal complex and Nafion suspension were combined. After reaching equilibrium the resulti ng mixture is used to coat the TCP electrode. Method B) The TCP electrode is coated with the Nafion membrane before immersing in a solution of the metal complex.

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97 These electrodes are extremely stable in so lvents commonly used in electrochemistry, such as water, propylene carbonate, nitromet hane and acetonitrile. They are however unstable in chlorinated solvents, rapidl y degrading in methylene chloride. MTCP-1. 200 L of a stock solution containing Nafion (0.25 wt %) and CpRu(amphos)2Cl (0.0167 wt %) dissolved in methanol was deposited on the surface of a TCP electrode. After drying, the modified electrode was washed with methanol and water before storing in aqueous KCl under an atmosphere of nitrogen. MTCP-2. 200 L of a stock solution containing Nafion (0.833 wt %) and CpRu(amphos)2(SnCl3) (0.0167 wt %) dissolved in me thanol was deposited on the surface of a TCP electrode. After drying, th e modified electrode was washed with acetonitrile before storing in acetonitril e under an atmosphere of nitrogen. MTCP-3. 200 L of a 2.5 wt % Nafion suspension was deposited on the surface of a TCP electrode. After dr ying, the modified electrode wa s immersed overnight in an acetonitrile or nitromethane solution of CpRu(amphos)2Cl (0.1 wt %). Electrodes modified by this method were stored in th is solution under an atmosphere of nitrogen when not in use. MTCP-4. These electrodes were prepared in an analogous manner to MTCP-3 with CpRu(amphos)2(SnCl3) as the metal complex. MTCP-5. These electrodes were prepared in an analogous manner to MTCP-3 with CpRu(Ph2PCH2CH2NMe2)2(SnPh3) as the metal complex.

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98 Table 4-6. Formal potentials for the m odified electrodes MTCP-1 to MTCP-5 Complex ElectrodeElectrolyte Epa (V vs NHE) E1/2 (V vs NHE) Ep (mV) ipa / ipc CpRu(amphos)2Cl ( 31 ) MTCP-1 0.1 M KCl / H2O 0.90 0.81 185 1.15 CpRu(amphos)2Cl ( 31 ) MTCP-1 0.1 M TBAT / MeOH 0.97 0.90 142 1.08 CpRu(amphos)2(SnCl3) ( 32 ) MTCP-2 0.1 M TBAT / CH3CN 1.38 1.36 42 1.03 CpRu(amphos)2Cl ( 31 ) MTCP-3 0.1 M TBAT / MeOH 0.92 0.85 146 1.06 CpRu(amphos)2Cl ( 31 ) MTCP-3 0.1 M TBAT / MeNO2 1.06 0.93 264 1.15 CpRu(amphos)2Cl ( 31 ) MTCP-3 0.1 M TBAT / CH3CN 0.82 0.77 110 1.13 CpRu(amphos)2(SnCl3) ( 32 ) MTCP-4 0.1 M TBAT / CH3CN 1.51 CpRu(amphos)2(SnCl3) ( 32 ) MTCP-4 0.1 M TBAT / MeNO2 1.73 CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 )MTCP-5 0.1 M TBAT / CH3CN 1.36

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99 99 Cyclic Voltammetry Cyclic voltammetry was used to probe the stability of CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 ), CpRu(amphos)2Cl ( 31 ) and CpRu(amphos)2(SnCl3) ( 32 ) in the modified electrodes. Electrodes modified with CpRu(amphos)2Cl ( 31 ) were stable in solutions of me thanol, acetonitrile, nitromethane and water, with no evidence of leaching. Th ese CVs were also very reproducible even upon repeated cycling and prolonged storag e. When placed in 0.1 M TBAT/PC the complex rapidly leached from the electrode surface into solution. No leaching was observed when the electrodes were placed in propylene carbonate without supporting electrolyte. This indicated that the cation of the elec trolyte was displacing the Ru complex from the Nafion matrix. Attempts at stabilizing the electrodes by varying the supporting electrolyte (NaBPh4, NH4PF6) were unsuccessful. Because of the rapid leaching observed in PC, this solvent was not used during further studies of the modified electrodes. When attached to the electrode surface, a single chemically reversible oxidation wave was observed for MTCP-1 and MTCP-3 (Table 4-6). This redox process was assigned to the Ru(II/III) couple of CpRu(amphos)2Cl ( 31 ). The reversibility of this electron transfer process is a good indication that the complex and its oxidized form are both stable within the Nafion matrix. When immobilize d, the Ru(II/III) couple of 31 is typically shifted by 30 to 80 mV with respect to the Ru(II/III) couple of the complex in solution (Table 4-2).

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100 Figure 4-9. Cyclic voltammograms of MTCP-2, electrode modified with CpRu(amphos)2(SnCl3) ( 32 ) under nitrogen in 3.5 mL of CH3CN / 0.1 M TBAT; Ag/Ag+ reference electrode; 50 mV/s scan rate. The CVs of MTCP-2 and MTCP-4 are very stable and reproducible when analyzed in the aprotic solvents nitromethane and acetonitrile. For MTCP-2 in acetonitrile the oxidation of CpRu(amphos)2(SnCl3) ( 32 ) is reversible (Table 4-6, Figure 4-9). The Nafion matrix stabilizes [CpRu(amphos)2(SnCl3)]+, allowing it to be reduced reversibly. This was unexpected since in solutio n and in MTCP-4, the oxidation of 32 is irreversible (Table 4-3 and 4-6). No redox waves were in itially observed in the CVs of MTCP-2 and MTCP-4 when analyzed in water or metha nol. The absence of the Ru(II/III) oxidation wave was thought to be as a result of the ca talytic current obscuri ng its presence. Upon repeated scans a redox couple sim ilar to the Ru(I I/III) couple of 32 is observed. This was the first indication that in the presence of methanol and water MTCP-2 and MTCP-4 may be unstable. 31P{1H} NMR was used to monitor the stability of CpRu(amphos)2(SnCl3)

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101 ( 32 ) in the Nafion suspensions prior to coating the TCP electrode. Based on the NMR studies complex 32 is stable for at least two days in the Nafion suspension, prior to preparing MTCP-2. The actual decomposition pathway for the immobilized complex is uncertain, but it seems to require the passage of current in a protic solvent. The decomposition was also observed when th e CV is performed in acetonitrile and nitromethane solutions containing methanol. One attempt at stabilizing the complex dur ing the CV studies in methanol was the use of CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 ) in the modified electrodes (MTCP-5). This attempt however was unsuccessful and MT CP-5 also degraded when analyzed in water and methanol. Summary A series of Ru/Sn complexes co ntaining the amphiphilic ligands Ph2PCH2CH2NMe2 and Ph2PCH2CH2NMe3BF4 was synthesized and studied. Complexes 28 29 31 and 32 are soluble and stable in both pr otic and aprotic solvents. Cyclic voltammetry of these complexes was perfor med in methylene chloride, acetonitrile, nitromethane, propylene chloride methanol and water. The electrochemical oxidation of methanol was performed with 28 29 31 and 32 in neat methanol. The products formed during the electrolysis ar e DMM and MF. The aminophosphine complexes ( 28 29 31 and 32 ) are not as efficient or selective as the TPPMS complexes ( 22 and 23 ) studied in chapter 3. The decreased ac tivity is attributed to th e stronger Ru-P bond and the decreased cone angle of the aminophosphine co mplexes. These two factors will inhibit phosphine dissociation, and retard the methanol oxidation reaction. Complexes containing the SnPh3 ligand CpRu(PPh3)2(SnPh3) ( 27 ) and CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 ), form smaller quantities of oxidation products

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102 than the corresponding SnCl3 complexes CpRu(PPh3)2(SnPh3) ( 20 ) and CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 29 ) respectively. This result indicates that the Lewis acidity of the tin(II) metal center is importa nt to the activity of the catalyst. Chemically modified electrode s were prepared with Nafion exchanged membranes containing CpRu(amphos)2Cl ( 31 ), CpRu(amphos)2(SnCl3) ( 32 ) and CpRu(Ph2PCH2CH2NMe2)2(SnPh3) ( 30 ). Electrodes modified with 31 were studied in solutions of water, methanol, nitromethane a nd acetonitrile. These el ectrodes were stable and no evidence of leaching was observed. Electrodes containing the heterobimetallic complexes could only be studied in nitrometha ne and acetonitrile. In solutions of water and methanol, the heterobimetallic complexes quickly decompose. Because of the instability of the electrodes in methanol a nd the retardation of th e oxidation reaction by nitromethane and acetonitrile, no catalytic studies were performe d with these electrodes.

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103 CHAPTER 5 EXPERIMENTAL PROTOCOLS General Considerations Standard Schlenk / vacuum techniques were used throughout. All NMR solvents were degassed via three freeze-pump-thaw cycl es and stored over 4 molecular sieves. 1H and 31P{1H}NMR spectra are referenced to th e residual proton in the deuterated solvent and to 85 % H3PO4, respectively. High-resolution mass spectrometry was performed by the University of Florida anal ytical service. Elemental analysis was performed by the Robertson Microl it Laboratories, Ma dison, NJ. ClCH2CH2N(CH3)2,208 cyclo -C5H5CH2CH2N(CH3)2,209 CpRu(PPh3)2Cl,210 Cp(PPh3)Ru( 1-dppm)Cl,211 CpRu( 2-dppm)Cl,212 CpRu( 2-dppe)Cl,212 CpRu( 2-dppp)Cl,213 RuCl2(PPh3)3,214 Ru( 2-Ph2PCH2CH2NMe2)2Cl2,215 (Ind)Ru(PPh3)2(SnCl3),216 CpRu(PPh3)2(SnCl3),125 ( 5-C5H4(CH2)2N(CH3)2H+)Ru( 2-dppm)Cl,217 and IrCl(CO)2(H2N(C6H4)CH3)218 were prepared as previously desc ribed. TPPMS was prepared using a slight modification of the published procedure.219 Tetra-n-butylammonium triflate (TBAT), and RuCl3xH2O were purchased from Sigma-Aldrich. (Ind)Ru(PPh3)2Cl was purchased from Strem Chemicals. Toray carbon paper (0.3 7 mm thickness) was purchased from fuelcellstore.com. Copper wire (0.5 mm diameter, 99.9999 %) was purchased from Alfa Aesar. All other starting materials were purchased in reagent grade purity and used without further purification.

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104 Electrochemistry Electrochemical experiments were perfor med at ambient temperature in a glove box under a nitrogen atmosphere using an EG&G PAR model 263A potentiostat/galvanostat. Cyclic voltammetr y (CV) was performed with a normal threeelectrode configuration consisting of a work ing electrode (glassy carbon 3 mm diameter or TCP electrode area 2 cm-2), a Pt flag counter electrode and a reference electrode. For experiments performed in 1,2-dichloroethane (DCE) or methanol, the reference electrode consisted of an acetonitrile solution of freshly prepared 0.01 M AgNO3 and 0.1 M TBAT along with a silver wire. The Ag+ solution and silver wire were contained in a 75 mm glass tube fitted at the bottom with a Vy cor tip. For aqueous solutions a Ag/AgCl reference electrode (Bioanalytical Systems) was used. Constant potential electrolysis was carried out with similar equipment excep t for the working electrode being replaced with a vitreous carbon electrode. All poten tials are reported vs. NHE and are not corrected for the junction potential of the reference electrode. The E0 values for the ferrocene/ferrocenium couple in the electrol ytes used is shown in Table 5-1. Table 5-1. Formal potentials of the ferrocene/ferrocenium couple Electrolyte Fc+/0 (V vs NHE)a 0.7 M TBAT / DCE 0.50 0.7 M TBAT/CH2Cl20.50 0.1 M TBAT/MeOH 0.50 0.1 M TBAT/PC 0.58 0.1 M TBAT/CH3CN0.41 0.1 M TBAT/MeNO20.48 a Recorded at ambient temperatur e, scan rates = 50 mV/s.

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105 Electrode Fabrication Toray carbon paper (TCP) electrodes were fa bricated as follows: TCP was cut into 1.5 cm x 1.0 cm blocks, treated with acet one, 0.1 M HCl and water to remove any impurities. The TCP blocks were then dried ov ernight at 60 C. Electrical contact to the TCP was made through a copper wire attached with a conductive silver paste. After curing overnight at 60 C, the electrode was cleaned as be fore with acetone, 0.1 M HCl and water, before drying at 60 C for 5 hour s. The silver electrical contact was then encapsulated with an insulating epoxy to give a TCP electrode with an area of approximately 2 cm-2. After curing overnight at 60 C the electrode was cleaned again as described above and stored in an inert atmosphere. Product Analysis Electrolysis products were analyzed by gas chromatography on a Shimadzu GC17A chromatograph containing a 15 m x 0.32 mm column of AT™-WAX (Alltech, 0.5 m film) on fused silica. The column was attached to the injection port with a neutral 5 m x 0.32 mm AT™-WAX deactivated guard column. The electrolysis products were quantitati vely determined with the use of n -heptane as an internal standard. Products were identifie d by comparison to authentic samples. Preparation of Modified Electrodes Method A. Stock solutions of Nafion (0.5 2.5 wt %) and Ru complex (0.1 – 0.5 wt %) were prepared by slowly adding methanol solutions of the Ru complex to a rapidly stirred suspension of 5 wt % Nafion. The re sulting mixture was le ft stirring under N2 overnight to allow the ion exchange proce ss to reach completion. The TCP electrodes were then coated with the Nafion/Ru mixture (50 L increments), and evaporation of the

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106 solvent assisted with a gentle flow of nitrog en. The electrodes were then dried at 60 C for 30 minutes before rinsing with methanol water and allowed to air dry at ambient temperature overnight. Electrodes modified by this method (MTCP-A) were stored under an atmosphere of nitrogen when not in use. Method B. TCP electrodes were coated with 200 L of a Nafion suspension (1 – 5 wt %) rinsed with water and drie d overnight at 60 C. The Nafion modified electrodes are then taken into the glove box before immersi ng overnight in a solution (0.1 – 0.5 wt %) of the Ru complex. Elect rodes modified by this method (MTCP-B) were stored in this soluti on under an atmosphere of nitr ogen when not in use. Synthesis CpRu(PPh3)(-Cl)(-dppm)HgCl2 (16) A 50 mL Schlenk flask was charged with mercury acetate (0.21 g, 0.65 mmol) and 20 mL of DCE. To this suspension, CpRu(PPh3)(Cl)( 1-dppm) ( 6 ) (0.56 g, 0.65 mmol) dissolved in 20 mL of DCE was slowly adde d while stirring. After two hours acetyl chloride (12 drops) dissolved in 20 mL of DCE was slowly added. All volatiles were removed in vacuo after an additional hour of stirring. The resulting yellow solid was then redissolved and filtered through Hyflo Super Cel with 50 mL of DCE. This orange solution was then concentrated to approxi mately 5 mL before hexanes (20 mL) was added. The resulting yellow solid was coll ected on a sintered glass frit and dried overnight at 80 C under vac uum. Yield: 0.59 g, 81 %. 1H NMR (CD2Cl2): 7.81 – 6.50 (m, 35H, Ph2PCH2P Ph2 + P Ph3), 4.85 (s, 5H, Cp), 3.25 – 2.95 (m, 2H, Ph2PC H2PPh2). 31P{1H} NMR (CDCl3): 39.9 (d, RuP Ph3, JPP = 40 Hz), 35.0 (dd, RuP Ph2CH2PPh2, JPP = 40 Hz, 10 Hz), 30.1 (d, HgP Ph2CH2PPh2, JPP = 10 Hz).

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107 CpRu(PPh3)(-Cl)(-dppm)Hg(OAc)2 (18) Mercury (II) acetate (0.03 g, 0.10 mmol) and 5 mL of CH2Cl2 was placed in a 25 mL Schlenk flask. The Schlenk flask was then fitted with an additi on funnel containing CpRu(PPh3)( 1-dppm)Cl (0.08 g, 0.10 mmol) in 5 mL of CH2Cl2. Approximately 10 minutes after the addition was complete, the mercury acetate was completely dissolved and stirring continued for an additional hour The solution was then filtered through Hyflo Super Cel before evaporating to dryness at low pressure. The resulting solid was then recrystallized from CH2Cl2/hexanes. Yield: 95 %. 1H NMR (CDCl3): 31P{1H} NMR (CDCl3): 41.9 (d, RuP Ph3, JPP = 43 Hz), 36.9 (dd, RuP Ph2CH2PPh2, JPP = 43 Hz, 28 Hz), 24.1 (d, Hg-PPh2CH2P Ph2, JPP = 28 Hz). CpRu(TPPMS)2Cl (22) In a 250 mL flask, CpRu(PPh3)2Cl (1.0 g, 1.4 mmol) and TPPMS (0.89 g, 2.3 mmol) in 100 mL of toluene were refluxed under N2 for two days. The resulting orange solid was then collected on a medium frit, wa shed with approximately 200 mL of diethyl ether and dried under vacuum at 80 C. Yield: 0.97 g, 90 %. 1H NMR (DMSO-d6): 7.72 – 7.52 (m, 4H), 7.25 – 7.08 (m, 24H), 4.07 (s, 5H, Cp). 31P{1H} NMR (DMSO-d6): 40.1 (s). HRMS (FAB): calc. for C41H33O6Na2P2RuS2 m/z 895.0033 [M – Cl2 H2O]+, found 894.9935. Anal. Calc. for C41H37O8Na2ClP2RuS2: C, 50.96; H, 3.86. Found: C, 50.71; H, 3.68. CpRu(TPPMS)2(SnCl3) (23) CpRu(TPPMS)2Cl (0.71 g, 0.76 mmol) and SnCl2 (0.17 g, 0.89 mmol) in 25 mL ethanol were stirred under N2 at room temperature overni ght. The solution was then evaporated to dryness and the resulting yello w solid recrystallized from ethanol/diethyl

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108 ether. Yield: 0.73 g, 85 %. 1H NMR (CD3OD): 7.86 – 7.70 (m, 4H), 7.35 – 7.08 (m, 24H), 4.65 (s, 5H, Cp). 31P{1H} NMR (CD3OD): 46.0 (s, TPPMS, 2JP,Sn = 422 Hz). Anal. Calc. for C41H37O8Na2Cl3P2RuS2Sn: C, 42.60; H, 3.23. Found: C, 42.87; H, 3.07. CpRu( 2-dppm)(SnCl3) (24) A 50 mL Schlenk was charged with CpRu( 2-dppm)Cl (0.59 g, 1.0 mmol), anhydrous SnCl2 (0.21 g, 1.1 mmol) and 40 mL of ethanol This orange mixture was then refluxed for 5 hours. The resulting bri ght yellow solid was then filtered and recrystallized from CH2Cl2/hexane before drying under vacuum at 60 C. Yield: 0.66 g, 85 %. 1H NMR (CDCl3): 7.62 – 7.28 (m, 20H, Ph2PCH2P Ph2), 5.16 (m, 1H, Ph2PC H PPh2), 5.08 (s, 5H, Cp), 4.76 (m, 1H Ph2PC H PPh2). 31P{1H} NMR (CDCl3): 8.3 (s, P Ph2CH2P Ph2). CpRu( 2-dppp)(SnCl3) (26) A 50 mL round bottom flask was charged with CpRu( 2-dppp)Cl (0.24 g, 0.39 mmol), anhydrous SnCl2 (0.09 g, 0.47 mmol) and 25 mL of ethanol before fitting with a reflux condenser. This orange mixture was th en refluxed overnight under an atmosphere of nitrogen. The resulting bri ght yellow solid was then colle cted on a sintered glass frit and washed with ethanol before drying in vacuo at 60 C. Yield: 0.29 g, 91 %. 1H NMR (CDCl3): 7.48 – 7.22 (m, 20H, Ph2PCH2CH2CH2P Ph2), 4.84 (s, 5H, Cp ), 2.8 – 2.7 (m, 4H, Ph2PC H2CH2C H2PPh2), 1.54 (s, 2H, Ph2PCH2C H2CH2PPh2). 31P{1H} NMR (CDCl3): 33.9 (s, P Ph2CH2CH2CH2P Ph2). HRMS (FAB): calc. for C32H31P2Ru m/z 579.0944 [M – SnCl3 -]+, found 579.2200.

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109 CpRu(PPh3)2(SnPh3) (27) A 100 mL Schlenk flask was charged with CpRu(PPh3)2(SnCl3) (1.0 g, 1.1 mmol) and 50 mL of benzene, before fitting with an addition funnel containing 2.4 mL of phenyllithium (1.8M in di-n-butylether). Ph enyllithium was then added dropwise to the yellow suspension, resulting in a purple solution. Stirring was continued for 4 hours at room temperature before quenching with 1 mL of ethanol. After removing the solvent, the resulting yellow solid was dried in vac uo for 2 hours. The yellow solid was then dissolved in approximately 100 mL of diethyl ether and filtered through a pad of Hyflo Super Cel before drying in vacuo at 60 C overnight. Yield: 1.02 g, 90 %. 1H NMR (CDCl3): 7.19 – 6.98 (m, 45H), 4.27 (s, 5H, Cp). 31P{1H} NMR (CDCl3): 53.0 (s, P Ph3, 2JPSn = 270 Hz). HRMS (FAB): calc. for C53H44P2RuSn m/z 964.0977 [MH+ – C6H6]+, found 964.0941. CpRu(Ph2PCH2CH2N(CH3)2)2Cl (28) A two necked 100 mL round bottom flask f itted with a reflux condenser and a rubber septum was charged with Ru( 2-Ph2PCH2CH2NMe2)2Cl2 (0.65 g, 0.95 mmol), cyclopentadiene (0.19 g, 2.8 mmol ) and 50 mL of ethanol. This red mixture was then refluxed for three days under an atmosphere of nitrogen. After refl uxing, the solvent was removed under vacuum and the resulting ora nge solid washed with 90 mL of n-hexanes before recrystallizing with CH2Cl2/n-hexanes. Yield: 0.50 g, 74 %. 1H NMR (CDCl3): 7.47 – 7.15 (m, 20H), 4.29 (s, 5H, Cp), 3.12 (m, 2H), 2.94 (m, 2H), 2.63 (s, 12H, N(C H3)2), 2.42 (m, 2H), 2.20 (m, 2H). 31P{1H} NMR (CDCl3): 36.6 (s, Ph2P CH2CH2NMe2). HRMS (FAB): calc. for C37H46ClN2P2Ru m/z 717.1872 [MH]+, found 717.1889.

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110 CpRu(Ph2PCH2CH2N(CH3)2)2(SnCl3) (29) A 25 mL Schlenk flask was charged with CpRu(Ph2PCH2CH2N(CH3)2)2Cl (0.84 g, 1.11 mmol), SnCl2 (0.33 g, 1.75 mmol) and 20 mL of 1,2dichloroethane. The resulting mixture was stirred at room temperature for two days before refluxing for 6 hours. After removing the solvent under vacuum, the orange solid was dissolved in CH2Cl2 and filtered through a pad of Hyflo Super Cel. A yellow solid was then precipitated with nhexanes before recr ystallizing with CH2Cl2/n-hexanes. Yield: 0.97 g, 96 %. 1H NMR (CDCl3): 7.44 – 7.19 (m, 20H), 4.71 (s, 5H, Cp), 3.09 (m, 4H), 2.86 – 2.74 (m, 14H), 2.56 (m, 2H). 31P{1H} NMR (CDCl3): 39.4 (s, Ph2P CH2CH2NMe2, 2JPSn = 412 Hz). HRMS (FAB): calc. for C37H45Cl2N2P2RuSn m/z 871.0500 [M-Cl-]+, found 871.0543. CpRu(Ph2PCH2CH2N(CH3)2)2(SnPh3) (30) A 50 mL Schlenk flask was charged with CpRu(Ph2PCH2CH2N(CH3)2)2(SnCl3) (0.25 g, 0.28 mmol) and 50 mL of toluene before cooling to -78 C. The Schlenk flask was then fitted with an addition funnel c ontaining 0.70 mL of phenyllithium (1.7M in din-butylether) and 2 mL of toluene. Phenylli thium was then added dropwise, resulting in the formation of a purple solution. Stir ring was continued for 4 hours at room temperature before quenching with 1 mL of et hanol. After drying in vacuo, the resulting yellow solid was dissolved in n-hexanes and f iltered through a pad of Hyflo Super Cel. Complex 30 was then isolated by chromatography on SiO2 with 99:1 (chloroform/triethylamine) as eluent. Yield: 0.19 g, 64 %. 1H NMR (CDCl3): 7.52 – 7.09 (m, 35H), 4.21 (s, 5H), 2.3 – 2.1 (m, 4H ), 1.81 (s, 12H), 1.6 – 1.7 (m, 4H). 31P{1H} NMR (CDCl3): 43.8 (s, Ph2P CH2CH2N(CH3)2, 2JPSn = 262 Hz).

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111 CpRu(Ph2PCH2CH2N(CH3)3BF4)2Cl (31) A 500 mL two-necked round bottom flask containing CpRu(PPh3)2Cl (1.00 g, 1.37 mmol) and 150 mL of toluene was fitted with a reflux condenser and a pressure equalizing addition funnel befo re heating to reflux. To the refluxing orange mixture, a solution of amphos (0.99 g, 2.8 mmol) in 50 mL of methylene chloride was added dropwise. After four days of reflux, th e solvent was removed under vacuum and the resulting yellow solid was washed with 200 mL of petroleum ether and 100 mL of toluene before recrystallizing from CH2Cl2 / diethyl ether. Yield: 0.96 g, 76 %. 1H NMR (DMSO-d6): 7.49 – 7.21 (m, 20H), 4.48 (s, 5H, Cp), 3.21 – 2.85 (m, 24H), 2.57 (m, 2H). 31P{1H} NMR (DMSO-d6): 35.9 (s, amphos). HRMS (FAB): calc. for C39H51BClF4N2P2Ru m/z 833.2294 [M-BF4 -]+, found 833.2287. CpRu(Ph2PCH2CH2N(CH3)3BF4)2(SnCl3) (32) CpRu(amphos)2Cl (0.20 g, 0.22mmol) and SnCl2 (0.50 g, 0.33mmol) in 50 mL of ethanol were refluxed under N2 overnight. The solution was then evaporated to dryness and the resulting yellow solid was recrystallized from ethanol/diethyl ether. Yield: 0.21 g, 88 %. 1H NMR (acetone-d6): 7.65 – 7.43 (m, 20H), 5.00 (s, 5H, Cp), 3.49 (m, 2H), 3.11 (s, 18H, N(C H3)2), 2.94 (m, 4H), 2.44 (m, 2H). 31P{1H} NMR (acetone-d6): 39.5 (s, Ph2P CH2CH2NMe3BF4, 2JP,Sn = 405 Hz). Ph2PCH2CH2N(CH3)2 1.25 g of Li chips and 100 mL of THF were placed in a 250 mL Schlenk flask fitted with a pressure equalizing addition funnel. To the vigorously s tirred Li suspension, Ph2PCl (10 g, 0.045 moles) in 50 mL of THF was sl owly added. After stirring at R.T. for 12 hours, the resulting Ph2PLi solution was transferred to a two necked round bottom

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112 flask fitted with a rubber septum and an addi tion funnel. While stirring the deep red Ph2PLi solution, ClCH2CH2N(CH3)2 (5.0 g, 0.036 moles) in 50 mL of THF was slowly added before heating for 12 hours at 60 C. The resulting mixture was then hydrolyzed with 50 mL of degassed water, before adding 20 0 mL of diethyl ether. The organic layer was extracted with 250 mL of water and dried over MgSO4 before the solvent was removed under vacuum to yield an oil. Pu rification of the oil was achieved using flash chromatography through a column of neutral al umina with diethyl ether as the eluent. Yield: 7.86 g, 84 %. The compound was identi fied by comparison to literature data.220 Ph2PCH2CH2N(CH3)3BF4 Me3OBF4 (1.65 g, 0.011 mol) and 80 mL of CH2Cl2 were added to a 250 mL Schlenk flask, fitted with a pressure equalizing addition funnel. The flask was then cooled to -98 C before a solution of Ph2PCH2CH2N(CH3)2 (3.01 g, 0.012 mol) in 30 mL of CH2Cl2 was added dropwise. When the addition was complete the mixture was stirred at -98 C for 5 hours then at rt overnight. The resulting white so lid was collected on a sintered frit and washed exha ustively with diethyl ether, before recrystallizing from CH2Cl2 / diethyl ether. Yield: 3.36 g, 84 %. 1H NMR (acetone-d6): 7.42 – 7.55 (m, 10H, Ph2P), 3.68 (m, 2H, Ph2PC H2CH2NMe3), 3.38 (s, 9H, Ph2PCH2CH2N Me3), 2.85 (m, 2H, Ph2PCH2C H2NMe3). 31P{1H} NMR (acetone-d6): -19.5 (s, Ph2P CH2CH2NMe3). [( 5-C5H4(CH2)2N(CH3)2H)Ru(-dppm)(-CO)2IrCl2]Cl A 100 mL round bottom flask was charged with ( 5-C5H4(CH2)2N(CH3)2H+)Ru( 2-dppm)Cl (1.3 g, 2.0 mmol), IrCl(CO)2(H2N(C6H4)CH3) (0.81 g, 2.0 mmol) and 50 mL of toluene. This mixture was then refluxed for 24 hrs and the resulting yello w precipitate collected on a sintered glass

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113 frit. The crude product was then placed into a Soxhlet extractor and impurities extracted overnight with benzene, before drying overnig ht in vacuo at 60 C. Yield: 1.25 g, 65 %. 1H NMR (DMSO-d6): 7.52-7.18 (m, 20H, Ph2PCH2P Ph2), 5.30 (s, 2H, Cp ), 5.07 (s, 2H, Cp ), 3.17 (m, 2H, Ph2PC H2PPh2), 2.70 (m, 10H, C5H4(C H2)2N(C H3)2H+). 31P{1H} NMR (d6-DMSO): 59.8 (d, Ru-Ph2P CH2PPh2, JPP = 59 Hz), 12.4 (d, IrP Ph2CH2PPh2, JPP = 59 Hz). IR (KBr) 1800, 1780 cm-1. HRMS (FAB) calcd for C36H37Cl2IrNO2P2Ru m/z 942.0349 [M-Cl-]+, found 942.0377. Crystallographic Structure Determination of CpRu(PPh3)(-Cl)(-dppm)HgCl2 (16) Data were collected at 173 K on a Siemens SMART PLATFORM equipped with a CCD area detector and a graphite monochromator utilizing MoK radiation ( = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the -scan method (0.3 frame width). The first 50 frames were remeasured at the end of data collection to monitor instrument and crystal stability (maximum correction on I was < 1 %). Absorption corrections by integration were applied based on measured indexed crystal faces. The structure was solved by the Direct Methods in SHELXTL5, and refined using full-matrix least squares. The non-H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal pos itions and were riding on their respective carbon atoms. The asymmetric unit consists of the complex and two dichloroethane molecules of crystallization. One of thos e molecules had one of its chlorine atoms disordered and was refined in two parts (Cl6 & Cl6'). Their site occupation factors were dependently refined to 0.67(2) for Cl, and c onsequently 0.33(2) for Cl 6'. A total of 581 parameters were refined in the final cycle of refinement using 10968 reflections with I >

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114 2 (I) to yield R1 and wR2 of 2.07 % and 5.23 %, respectively. Refinement was done using F2.

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128 BIOGRAPHICAL SKETCH Corey Ricardo Carlo Anthony was born in Kingston, Jamaica on December 31st, 1976. His interest in the sciences was sparked at an early age by his sisters and their toy chemistry kit. Corey spent his formative ye ars at St. Theresa Prep aratory School before attending St. George’s Colle ge High School where his love for chemistry took root. After completing high school Corey went on to pursue a tertiary level education at the University of the West Indies at Mona. He thoroughly enjoyed his college years and graduated in 1998 with a Bachelor of Scien ce degree in pure and applied chemistry. Corey then got his first full time job at the Jamaica Forensic Science Laboratory as a forensic science examiner. He worked at th e forensic lab for two years before enrolling at the University of Florida. In spring of 2001 he joined the McElwee-White research group and began his Ph.D. studies in organom etallic chemistry. After six years of research, he graduated from the University of Florida with a Doct orate of Philosophy in chemistry.


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Permanent Link: http://ufdc.ufl.edu/UFE0013887/00001

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Title: Study of Homogeneous and Heterogenized Ruthenium / Tin Heterobimetallic Complexes: Synthesis, Electrochemistry and Catalytic Properties
Physical Description: Mixed Material
Copyright Date: 2008

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Material Information

Title: Study of Homogeneous and Heterogenized Ruthenium / Tin Heterobimetallic Complexes: Synthesis, Electrochemistry and Catalytic Properties
Physical Description: Mixed Material
Copyright Date: 2008

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STUDY OF HOMOGENEOUS AND HETEROGENIZED
RUTHENIUM / TIN HETEROBIMETALLIC COMPLEXES:
SYNTHESIS, ELECTROCHEMISTRY AND CATALYTIC PROPERTIES















By

COREY R. ANTHONY


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA


2006

































Copyright 2006

by

Corey R. Anthony


























This dissertation is dedicated to my grandfather, Leonard Legister,
September 30th, 1900 March 4th, 2004.
You may be gone POPPA but you will never be forgotten.















ACKNOWLEDGMENTS

I would like to first thank God because with him all things are possible.

I would now like to acknowledge the strong women who have had a positive

impact in my life. First and foremost I thank my mother, a remarkable single parent who

made countless sacrifices in raising three children. To her I owe my strong work ethic,

drive for education and will always love unconditionally. I want to also acknowledge my

lovely wife for all her love, support and patience which kept me focused during many

endless nights of research. To her I owe a tremendous debt of gratitude for being my

rock these last two years. I also wish to thank my sisters Charmaine and Cheryl and my

cousin Heather for always being there and making this PhD dream of mine a reality.

I would now like to thank my advisor, another strong woman Dr. Lisa McElwee-

White. To her I express gratitude for all the discussions and advice during the six years I

have apprenticed with her. Under her tutelage I was able to grow both as a chemist and

as a person. I'd like to also thank the McElwee-White group members past and present.

Special thanks from me go out to Dr. Keisha-Gay Hylton, Dr. Corey Wilder, Dr. Ying

Yang and Daniel Serra. I would also like to thank Dr. Khalil Abboud for solving the X-

ray crystal structures presented in this dissertation.
















TABLE OF CONTENTS

page

A C K N O W L E D G M E N T S ................................................................................................. iv

LIST OF TABLES ..................._......... .................... ......... ...... ....... ... viii

LIST OF FIGURES ............................... ... ...... ... ................. .x

ABSTRACT .............. ..................... .......... .............. xii

CHAPTER

1 LITERATURE REVIEW ............... .................... .... ......... .....................1

Oxidation of Organic M olecules .................... ....................... .... ....... .... ...........1
Oxidation of A lcohols ................................................................................... 2
Electrochemical Oxidation of Methanol in Fuel Cells ..............................................3
M e ch an ism ....................................................... ................ .. 4
Binary Electrocatalysts ........................................ ... ............... ... ..........
Pt/Ru binary anodes ....................................... ............ ........7
C om binatorial Screening .................................................................. ... ............ 8
Reaction Interm ediates ...................... ............... ......... ... ...............
Electrochemical Oxidation of Alcohols by Metal Complexes .............. ................9
Ruthenium Electrocatalysts ...................................... ......................... .... ...... 11
R activity of B im etallic Com plexes.................................... .................................... 13
Heterobimetallic Electrooxidation Catalysts................................. ...................... 16
Product Form action .......... .. ................................ ........ ........ ............ 18
Bulk Electrolysis of Methanol ................. .......... ....................20
Summary ............... .....................................................21


2 SYNTHESIS AND ELECTROCHEMICAL PROPERTIES OF A RUTHENIUM /
MERCURY HETEROBIMETALLIC COMPLEX .............................................22

Introduction.............. .......... .. ...... ................... 22
Role of the Non-Ru M etal Center ......... .... ... ............................ .............. 25
Lewis Acid Catalysts ........................ ........................ ........ 27
Classification of Lew is A cids.................................... ............................. ....... 29
Lewis Acidic Properties of M ercury Complexes ...............................................31
C hem istry of M ercury ........... ............................................................................ ... 33


v









M mercury C analyzed R eactions................................ ........................................33
Synthesis and Characterization of CpRu(PPh3)([-C1)(-dppm)HgC2 ......................34
Attempted Synthesis of CpRu(PPh3)([-C1)(p-dppm)HgCl2 (16)......................34
Synthesis of CpRu(PPh3)([-C1)(p -dppm)HgCl2 (16) ..........................................36
Synthesis of CpRu(PPh3)(t-C1)(p-dppm)Hg(OAc)2 (18) .................................36
Analysis of CpRu(PPh3)([-C1)(ip-dppm)HgCl2 Structure .................................37
C y clic V oltam m etry ...................................................................................... .. 3 9
Sum m ary ..................................... ................................... .......... 41


3 THE SELECTIVE PARTIAL ELECTROOXIDATION OF METHANOL TO
DIMETHOXYMETHANE WITH RUTHENIUM/TIN HETEROBIMETALLIC
C O M P L E X E S ....... .. .. .... .......... ................................ .. ................ .. 43

Introduction ....................................... .................. .................... .. 43
Chemistry of Tin .......................................43
Bonding in Heterobimetallic Tin (II) Complexes ............................................44
Synthesis of Ruthenium / Tin (II) Complexes ...............................................44
Heterobimetallic Tin (II) Catalysts ........................................ ...............45
M ethanol as a Chem ical Feedstock ........................................ ........................ 48
Electrochemical Synthesis of Organic Molecules .................................................51
S y n th esis ........................................ ....... ...... .................. .... ........ 5 5
Synthesis of CpRu(TPPMS)2C1 (22) .........................................................55
Synthesis of CpRu(TPPMS)2(SnCl3) (23)..................................... .................57
Synthesis of CpRu(Q2-dppm)(SnC13) (24)........................................................58
Synthesis of CpRu(l2-dppp)(SnC13) (26)............................ ..................59
N M R D ata ......................................................................................................... 60
C yclic V oltam m etry.......... .............. .... ......................... ........... ...... .. ............. 61
Electrochemical Oxidation of Methanol ............ ...............................................64
Electrochemical Oxidation of W et M ethanol .............. .............................................69
Electrochemical Oxidation of Dimethoxymethane ......................................................71
Sum m ary ............... ..................................... ........................... 7 1


4 CHEMICALLY MODIFIED ELECTRODES CONTAINING IMMOBILIZED
RUTHENIUM/TIN HETEROBIMETALLIC COMPLEXES............................. 73

Introduction ................................................. 73
Nafion ...................................... ...........................73
N afion Supported M etal Catalysts.................................. ....................... 74
Chem ically M odified Electrodes ........................................ .......................... 76
Electrodes Modified with Ruthenium Complexes ...........................................77
Preparation of CM E ................. .... .......... ............... .... .... .. ............ 78
Electrodes Modified with Bimetallic Complexes....................................79
S y n th esis .................................................... ............................. ........ 8 1
Synthesis of CpRu(PPh3)2(SnPh3) (27) ........................................ ....................81
Synthesis of CpRu(Ph2PCH2CH2NMe2)2C1 (28)..............................................82









Synthesis of CpRu(Ph2PCH2CH2NMe2)2(SnCl3) (29) ........................................82
Synthesis of CpRu(Ph2PCH2CH2NMe2)2(SnPh3) (30) ........................................83
Synthesis of CpR u(am phos)2C1 (31) ........................................ .....................83
Synthesis of CpRu(amphos)2(SnCl3) (32) .......................................................84
NMR Data .............................................................................. 85
H om ogeneou s Studies ........................... ........ .................. ........ .. ................86
Cyclic Voltammetry ......................................... ........... ............. 86
Electrochemical Oxidation of Methanol .................................. .................90
H heterogeneous Studies............... ......... ...... ..................... .. ........ .. ............. .96
Preparation of Modified Toray Carbon Paper (MTCP) Electrodes...................96
C yclic V oltam m etry ....................... .. .................... ... ...... .. .... ...........99
S u m m a ry ......................................... .................................................1 0 1


5 EXPERIMENTAL PROTOCOLS ........................................ ....................... 103

G general C onsiderations.................................................. ............................... 103
Electrochem istry .................................................. ... ...... .. ........ .... 104
E lectrode Fabrication......... ..................................................... ............... 105
Product Analysis .............. .... ..... .. .................. .. .... ............ 105
Preparation of Modified Electrodes........ ........................ ............. 105
Synthesis ............. ......... .................. .. .. ................................. 106
CpRu(PPh3)(a-Cl)(a-dppm)HgCl2 (16) .....................................................106
CpRu(PPh3)(La-C1)(at-dppm)Hg(OAc)2 (18)................................ ................107
CpR u(TPPM S)2C 1 (22)............................................. ............................. 107
CpRu(TPPMS)2(SnCl3) (23) .................. ......... .... ................... 107
CpR u( 2 -dppm )(SnC 3) (24)........................................ .......................... 108
CpR u( 2 -dppp)(SnC13) (26)........................................ ........................... 108
CpRu(PPh3)2(SnPh3) (27) ............................................... .............. ................ 109
CpRu(Ph2PCH2CH2N(CH3)2)2C1 (28) ......................................................109
CpRu(Ph2PCH2CH2N(CH3)2)2(SnCl3) (29)......................................................110
CpRu(Ph2PCH2CH2N(CH3)2)2(SnPh3) (30) ...................................................110
CpRu(Ph2PCH2CH2N(CH3)3BF4)2C1 (31) ............................................... ......... 111
CpRu(Ph2PCH2CH2N(CH3)3BF4)2(SnCl3) (32)............................ ..................111
Ph2PCH 2CH 2N (CH 3)2 ................................................ .................... ......... 111
Ph2PCH 2CH 2N (CH 3)3BF4 ................ ........................................... 112
[( 15-CsH4(CH2)2N(CH3)2H)Ru(a-dppm)(a-CO)2rCl12]C ............... .................112
Crystallographic Structure Determination of
CpRu(PPh3)([t-Cl)([t-dppm)HgCl2 (16)................................ .......... ..................113


LIST OF REFEREN CES ........................................................... .. ............... 115

BIOGRAPH ICAL SKETCH .............................................. ..... .......................... 128















LIST OF TABLES


Table pge

1-1 Catalytic oxidation of 1-phenylethanol .................................................. 16

1-2 Formal potentials for complexes 3, 4, 5 and 7 .............................. ................... 18

1-3 Bulk electrolysis data for the oxidation of methanol by 3 7..............................20

2-1 Form al potentials for complexes 8 14......................................... ............... 24

2-2 Bulk electrolysis data for the oxidation of methanol by 8 14..............................25

2-3 Selected N M R data for com plexes 16 18 ........................................ ..................37

2-4 Selected bond distances (A) and angles (deg) for
CpRu(PPh3)(t-Cl)(t-dppm)HgCl2 (16) .............................................. ............... 38

2-5 Crystal data and structure refinement for CpRu(PPh3)(t-C1)(t-dppm)HgCl2 (16) .39

3-1 Selected ionization potentials........................................................ ............... 44

3-2 TEMPO mediated electrooxidation of carbohydrates................................. 53

3-3 Selected NMR data for complexes 19 26.......................................................60

3-4 Form al potentials of complexes 19 26 ...................................... ............... 61

3-5 Bulk electrolysis data for the oxidation of methanol by 19 21 and 24 26...........66

3-6 Bulk electrolysis data for the oxidation of methanol by 22 and 23..........................68

3-7 Selective partial oxidation of m ethanol ............................ .......... .....................69

3-8 Bulk electrolysis data for the oxidation of wet methanol by 20, 21 and 23.............70

4-1 Selected NMR data for complexes 27 32....................................................85

4-2 Form al potentials of com plexes 27 32 ........................................ .....................87

4-3 Bulk electrolysis data for the oxidation of methanol by 27 32.............................91









4-4 Bulk electrolysis data for the oxidation of methanol by 28 and 29..........................94

4-5 Donor number of selected Lewis bases ...................................... ...............96

4-6 Formal potentials for the modified electrodes MTCP-1 to MTCP-5 ....................98

5-1 Formal potentials of the ferrocene/ferrocenium couple ............. ............. 104
















LIST OF FIGURES


Figure pge

1-1 Polarization data for Pt/M alloys at 60 C...................................... ............... 6

1-2 Cyclic voltammograms of 3 ....................... ........................ 19

2-1 Structure of compounds 3 5 and 8 14........... .............................................23

2-2 References to "Lewis acid" in the scientific literature...........................................27

2-3 Structure of trimeric perfluoro-ortho-phenylene mercury ................. ..............32

2-4 Unrefined crystal structure of [CpRu(PPh3)(r2-dppm)] [ZnC13]- (17) ...................35

2-5 Thermal ellipsoids drawing of the molecular structure of
CpRu(PPh3)(La-C1)(at-dppm)HgCl2 (16) .............................................. ...............38

2-6 Cyclic voltamm ogram s of 16 .........................................................................41

3-1 Structure of com pounds 19 26 ........................................ ......................... 56

3-2 Cyclic voltamm ogram s of 19 .........................................................................62

3-3 Cyclic voltammograms of 20 .......................................................... .......... 63

4-1 Structure of N afion ............. ............. ................. ....................... .......................73

4-2 Cluster-network model for hydrated Nafion ...................................................75

4-3 References to "chemically modified electrodes" in the scientific literature ............80

4-4 Structure of com pounds 27 32 ........................................ ......................... 81

4-5 Cyclic voltammograms of 20 .......................................................... .......... 88

4-6 Formation of DMM during the electrooxidation of methanol .............................92

4-7 Formation of MF during the electrooxidation of methanol............... ...............92

4-8 Cyclic voltammograms of 32 .......................................................... .......... 95









4-9 Cyclic voltammograms of MTCP-2......................................100















Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy

STUDY OF HOMOGENEOUS AND HETEROGENIZED
RUTHENIUM / TIN HETEROBIMETALLIC COMPLEXES:
SYNTHESIS, ELECTROCHEMISTRY AND CATALYTIC PROPERTIES


By

Corey R. Anthony

May 2006

Chair: Dr. Lisa McElwee-White
Major Department: Chemistry

This dissertation describes the synthesis, electrochemistry and catalytic properties

of a series of Ru/Sn complexes. A single oxidation wave, attributed to the Ru(II/III)

couple was observed in the cyclic voltammograms of the Ru/Sn complexes. The

electrocatalytic properties of these complexes were investigated during the

electrooxidation of methanol. The oxidation products observed are dimethoxymethane

(DMM) and methyl format (MF). The formation of DMM is favored when the catalysis

is performed with the Ru/Sn complexes. The selectivity of the catalysts can be tuned by

varying the anodic potential. The highest current efficiency (92.4 %) and selectivity (100

%) were obtained from the electrooxidation of methanol with CpRu(TPPMS)2(SnCl3)

(23). Chemically modified electrodes were also prepared by attaching Ru/Sn complexes

to the electrode surface. The electrochemical properties and stability of these

heterogenized complexes were studied using cyclic voltammetry.









A novel Ru/Hg complex CpRu(PPh3)(t-C1)(t-dppm)HgCl2 (16) was synthesized

and characterized. X-ray crystallography revealed a unique chloride and dppm linker in

16, the first time a Ru/Hg complex was isolated with these bridging moieties.














CHAPTER 1
LITERATURE REVIEW

Oxidation of Organic Molecules

In inorganic chemistry, oxidation is clearly defined as the loss of an electron by an

atom, molecule or ion accompanied with an increase in the formal oxidation state. For

organic chemists the concepts of oxidation states and electron transfer are less easily

applied, hence the definition of oxidation differs slightly from inorganic to organic

chemistry. Organic chemists have defined the oxidation of an organic molecule as either

1) the loss of hydrogen or 2) the replacement of hydrogen with a more electronegative

atom such as oxygen or a halogen.

The oxidation of organic molecules has a long history1 stemming to the 1780's and

Lavoisier's explanation of combustion. Observations in the 19th century linked the

deterioration of many organic materials such as rubber and natural oils to the adsorption

of dioxygen. The control of oxidation is desirable not only for inhibiting the degradation

of commercially important materials such as plastics, gasoline, and rubbers but also for

promoting the selective oxidation of hydrocarbon feedstocks such as olefins, alkanes and

aromatic hydrocarbons.

The first observation of a catalyzed oxidation reaction is attributed to Davy who

showed in 1820 that ethanol is oxidized to acetic acid (Eq. 1.1) in the presence of
[Pt]
CH3CH2OH + 02 l CH3COOH + H20 (1.1)

platinum. Since then the scope of the catalyzed oxidation reaction of organic molecules

has grown tremendously, becoming basic to organic chemistry and the petrochemical









industry. Catalytic oxidation of ethylene to acetaldehyde (Eq. 1.2, Wacker process) was

the first industrial scale reaction that used an organopalladium catalyst. The catalytic

[PdC14]2
CH2= CH2 + H20 [PdCl CH3CHO
CuCl2 (1.2)

oxidation of organic molecules is now widely used in the synthesis of fine chemicals.

These reactions are now well understood and can be utilized in synthesizing a wide array

of functional groups (Scheme 1-1).2

[MoVI] i0
RCH2CH--CH2



OH OH
RCH2CH= CH2 [OsVIII ]
+ RCH2CH-CH2
(H3C)3COOH


OH

[ SeW ]
[ ] RCHCH CH2

Scheme 1-1. Adapted from reference 2.

Oxidation of Alcohols

The selective oxidation of alcohols to the corresponding aldehyde, ketone or

carboxylic acid is of significance not only to fundamental research but also for

commercial manufacturing processes. Traditionally the oxidation of alcohols is

performed with high oxidation state metal reagents such as chromium (VI), Mn (VI) and

ruthenium (VIII). These methods have been reviewed extensively2'3 and will not be

covered within this dissertation. Another area of emphasis is the use of transition metal

catalysts along with a chemical co-oxidant such as oxygen,4-9 peroxide7's'10 or an amine









N-oxide.11'12 The above transformations have also been extensively studied and are

beyond the scope of this review. One area which has recently received significant

interest from the scientific community is the electrochemical oxidation of alcohols. The

literature on electrochemical oxidation of alcohols can be roughly grouped into two sets:

heterogeneous13,14 (fuel cell) and homogeneous studies.

Electrochemical Oxidation of Methanol in Fuel Cells

Fuel cells have been postulated as the power generation system of the immediate

future, poised to replace not only internal combustion engines15'16 but also advanced

alkali16'17 batteries. Due to their simplicity, high energy efficiency and low pollution,

direct methanol fuel cells (DMFCs) are especially suited for use in portable electronic

devices.16,17 In DMFCs aqueous methanol is electrochemically oxidized at the anode

(Eq. 1.3) to CO2

Anodic Reaction: CH3OH + H20 CO2 + 6 H+ + 6 e- (1.3)

while oxygen is reduced at the cathode (Eq. 1.4) to form water.

Cathodic Reaction: 3/2 02 + 6 H+ + 6e-- 3 H20 (1.4)

When combined, the two half reactions result in an electromotive force of 1.18 V for the

overall reaction (Eq. 1.5).

Overall Reaction: 3/2 02 + CH3OH -- CO2 + 2 H20 AE= 1.18 V (1.5)

The mechanism for this oxidation has been reviewedl8'19 extensively and can be

summarized in two key steps:

Physisorption and dehydrogenation of methanol on the electrode surface
Formation of CO2 from adsorbed carbonaceous intermediates









Very few electrode materials are capable of performing both reactions, and of these only

platinum and platinum based electrodes have displayed any encouraging activity and

stability in an acidic medium.

Mechanism

The surface catalyzed electrooxidation of methanol has been studied

exhaustively,1820-22 and because of this the reaction mechanism is now well understood.

The mechanism was elucidated using a variety of electrochemical and spectroscopic

methods. These methods include cyclic voltammetry, steady-state galvanostatic

polarizations, chronoamperometry, mass spectrometry, FTIR, XAS, etc.23-25 In-situ

spectroscopic experiments were very instrumental in examining adsorbed species and for

identifying intermediates formed during the reaction. By combining the results of cyclic

voltammetry, in-situ ellipsometry, XAS, and in-situ FTIR experiments, the reaction steps

below were proposed. The reaction is thought to initially proceed through a series of

dehydrogenation steps to adsorbed CO (Eq 1.6 1.9).1s,20-22 Adsorbed CO is a widely

accepted intermediate of methanol oxidation, and its presence has been observed with the

aid of various in-situ infrared spectroscopy techniques.26-28 CO and other carbonaceous

intermediates can then be oxidized to carbon dioxide and desorbed from the electrode

surface by reacting with adsorbed water (Eq 1.10 1.12).

The electrochemical oxidation of methanol on Pt is a complicated reaction

involving several steps; chemisorption of methanol and water, dehydrogenation of

methanol, interaction between adsorbed CO and OH species and the formation of









CO2.20'21 At potentials below 0.7 V (the potential region of interest) the rate determining

step (RDS) on Pt anodes was shown to be the dissociative chemisorption of water

(Eq 1.10).

CH3OH + Pt (s) > Pt-CH2OH + H+ + e (1.6)

Pt-CH2OH + Pt (s) > Pt2-CHOH + H+ + e- (1.7)

Pt2-CHOH + Pt (s) > Pt3-CHO + H + e- (1.8)

Pt3-CHO Pt-CO + 2 Pt (s) + H+ + e- (1.9)

H20 + Pt (s) Pt-OH + H + e- (1.10)

Pt-CO + Pt-OH Pt-COOH (1.1la)

Pt-CO + H20 Pt-COOH + H+ + e (1.llb)

Pt-COOH Pt (s) + C02 + H+ + e (1.12)

Presently DMFCs are faced with a few challenging problems, foremost of which is

that the overall reaction is very slow. The electrochemical oxidation of methanol

(Eq. 1.5), though thermodynamically favored, is a kinetically sluggish reaction even at

high catalyst loading. On the other hand, the electrooxidation of hydrogen (a

thermodynamically similar reaction) is very fast at low catalyst loading. The formation

of stable intermediates (Eq. 1.6 1.9)29,30 is responsible for the poor kinetics of the

methanol oxidation reaction. Adsorbed CO in particular is strongly bound to the surface

of Pt requiring a high overpotential (approximately 0.5 V vs NHE) in order to obtain a

reasonable current density. Based on these studies it is now accepted that an active

surface for methanol electrooxidation must:

"Activate" water at low potentials
Be labile to CO chemisorption
Catalyze the oxidation of CO to CO2










Binary Electrocatalysts

Although there has been moderate success with Pt anodes,3133 the rapid poisoning

of the surface with CO has made these electrodes inadequate for use in DMFCs. This

decision led to an intensive search for other materials that can improve the performance

of the Pt anode during the methanol oxidation process. Several methods have been

investigated for promoting the formation of CO2 (Eq. 1.10 1.12). One method involves

alloying Pt with a second metal, to accelerate the RDS. Since the dissociative

chemisorption of water (Eq. 1.10) is the RDS, Pt was alloyed with oxophilic metals in

order to increase the reaction rate. Alloys of Pt and an oxophilic metal have been

investigated as electrocatalysts for over 40 years. Beneficial effects have been observed

for Pt/Sn,34'35 Pt/Ir,36 Pt/W37-40 and Pt/Ru28'41-44 electrodes. Studies of Pt alloyed with

such metals shows that Ru has by far the largest catalytic effect18 (Figure 1-1).




0.9 Pt/Pd Pt/Au

0.8 Pt Pt/Os

0.7

0.6

0.5
Pt/Ru
0.4
0.3

0 50 100 150 200 250

Current / mA mg-1

Figure 1-1. Polarization data for Pt/M alloys at 60 OC in 2.5 M H2SO4 / 1 M CH3OH.
Adapted from reference 18.









Pt/Ru binary anodes

Considerable effort has been expended to clarify the role of Ru in Pt/Ru binary

electrodes. Of the mechanisms proposed, the bifunctional theory has gained general

acceptance.44-46 According to this mechanism, the Pt sites are responsible for the

chemisorption and dehydrogenation of methanol, while the Ru sites are responsible for

water activation (Eq. 1.13 1.14). This is supported by the fact that the discharging of

water on Ru occurs at 0.2 V, while the chemisorption of methanol on Pt is favored over

Ru.

H20 + Ru (s) Ru-OH + H+ + le (1.13)

Pt-CO + Ru-OH Pt(s) + Ru (s) + C02 + H + le- (1.14)

In-situ CO stripping voltammetry was used to evaluate the active surface area,

intrinsic catalytic effect and the surface composition of the anode. An anodic shift of the

peak potential was observed for the CO stripping voltammograms of the Pt/Ru

electrodes. This shift combined with the improved catalytic activity provides clear

evidence that on Pt/Ru binary electrodes CO removal is the RDS. The optimal Pt:Ru

ratio is still being aggressively investigated, and remains a source of some controversy.

At high temperatures (90 130 C) and on a carbon support it has been shown that the

optimal Ru content is 50 mole %.47 It is thought that at 50 % coverage the intrinsic rate

constant is maximized.

The alloying of Pt with non-noble metals, most notably Re48 and Mo, has been

reported to result in a strong enhancement of the methanol oxidation reaction. The

effectiveness of binary electrodes, especially Pt/Ru, has resulted in the recent

investigation of ternary Pt/Ru/Sn,49 Pt/Ru/Mo49 and Pt/Ru/W49'50 as well as quaternary

systems Pt/Ru/Os/Ir,41'51'52 Pt/Ru/Mo/W53 and Pt/Ru/Sn/W.54 Only a slight to moderate









improvement in activity was observed for these systems, relative to the Pt/Ru binary

electrode.

Combinatorial Screening

After thirty years of research, the Pt/Ru (50/50) binary alloy remains one of the

more active electrocatalysts for the methanol oxidation reaction. This lack of a

breakthrough and the high cost of the precious metals have made electrocatalysts a prime

target for combinatorial screening. Combinatorial chemistry and high-throughput

screening have revolutionized drug discovery and the pharmaceutical industry. These

complementary technologies are now used for the preparation and evaluation of large

numbers of formulations. Combinatorial screening of inorganic material has been used

for almost thirty years. This method has been instrumental in characterizing new

materials and in the development of new catalysts.

Combinatorial searches for electrocatalysts by current voltage methods are

extremely cumbersome, especially for large sample sizes. This obstacle was

circumvented in 1998 by Mallouk52 who monitored the cell reactions via a fluorescence

signal. In 1999 Ward55 expanded on this method and used an automated multi-electrode

array to perform the combinatorial screening. These methods have since been applied by

other researchers and have led to ternary and quaternary electrode materials that display

greater catalytic activity than Pt/Ru electrodes.

Reaction Intermediates

Although the complete oxidation of methanol to carbon dioxide is desired for fuel cell

applications, other species are often formed leading to a decrease in the fuel efficiency.

Frequently observed by-products of methanol oxidation include formaldehyde (Eq. 1.15)









and formic acid (Eq. 1.16). These products can undergo a condensation reaction to form

dimethoxymethane (DMM) (Eq. 1.17) and methyl format (MF) (Eq. 1.18).

CH30H > H2CO + 2 H + 2 e (1.15)

H2CO > HCOOH + 2 H+ + 2 e (1.16)

H2CO + 2 CH30H > CH2(OCH3)2 + H20 (1.17)

HCOOH + CH30H > HCOOCH3 + H20 (1.18)

The current efficiency and product ratio were shown to be dependent on several variables

such as temperature, anodic potential, mass transport and the catalyst type.56'57 For

example when the electrolysis of methanol is performed on a smooth Pt electrode at

ambient temperature the incomplete oxidation products formaldehyde and formic acid are

preferred.58 However when a high surface area platinized Pt electrode was used the

complete oxidation to carbon dioxide was favored.58 The condensation products DMM

and MF were observed in the anode exhaust of DMFCs operating at high temperatures

and methanol concentration.

Electrochemical Oxidation of Alcohols by Metal Complexes

The electrochemical oxidation of alcohols using a catalyst in solution is an example

of an indirect electrochemical process. It is termed indirect because it is the mediator

(metal complex) not the substrate (alcohol) that is oxidized at the electrode surface

(Scheme 1-2). After undergoing this activation the mediator reacts in bulk solution with

the substrate, regenerating the reduced metal complex and forming the oxidized substrate.










Metal Substrate Product
Complex (Ox)
(Ox)




e
Metal Substrate
Complex (Red)
(Red)
Electrode Bulk
Surface Solution

Scheme 1-2. Adapted from reference 59.

There are two means by which the mediator can oxidize the substrate during the

homogeneous reaction:

1. "Redox Catalysis"59 in which the mediator merely plays the role of an
electron carrier (Scheme 1-3), transferring electrons to the substrate via an
outer sphere process

[ M ](red) M [M](ox) + ne

[ M ](ox) + Substrate(red) [ M ](red) + Substrate(ox)

Substrate(ox) Product

Scheme 1-3.

2. "Chemical Catalysis"59 in which the mediator reacts with the substrate to
form an adduct (Scheme 1-4) before electron transfer occurs

[ M ](red) [ M ](ox) + ne

[ M ](ox) + Substrate(red) [ M- Substrate ](ox)

[ M- Substrate ](ox) Product + [ M ](red)

Scheme 1-4.

In this dissertation only the chemical catalysis (often referred to as electrocatalysis) will

be considered.









Ruthenium Electrocatalysts

Ruthenium polypyridyl complexes are suited as electrooxidation catalysts due to the high

stability and accessibility of multiple oxidation states, tunable redox potentials by varying

ligands and the possibility of multiple electron transfers. The electrochemical oxidation

of alcohols has been extensively studied with ruthenium polypyridyl catalysts.60-68

Significant contribution to this area has been made by Meyer, who in 1978 observed the

2e- reduction of a Ru complex accompanied by oxidation of triphenylphosphine to

triphenylphosphine oxide (Scheme 1-5).63 The pyridine ligand however, is not suited to

prolonged use and eventually dissociates, leading to an inactive oxo bridged dimer. The

instability of the pyridine ligand was eventually overcome by replacing it and a

bipyridine with the terpyridine (trpy) ligand.65 Of all the polypyridyl complexes

investigated as electrocatalysts, [(trpy)(bpy)Ru"(OH2)]2+ has attracted the most interest.


[(bpy)2pyRuVO ]2+ + PPh3 fast ] [ (bpy)2pyRu (OPPh3)]2+
slow
-slow [ (bpy)2pyRul(CH3CN)]2+ + O = PPh3
CH3CN

Scheme 1-5. Adapted from reference 63.

The Ru(II) aquo complex can undergo two reversible proton coupled 1 e- oxidation steps

to generate the versatile oxidant [(trpy)(bpy)RulV(0)]2+ (Eq. 1.19 -1.20).

[ (trpy)(bpy)RuI(H2) ]2+ [ (trpy)(bpy)RuIII(OH) ]2+ + e- + H+ (1.19)


[ (trpy)(bpy)Ru"'(OH) ]2 [ (trpy)(bpy)RuVO ]2+ + e- + H+ (1.20)

As an oxidant [(trpy)(bpy)RuIV(O)]2+ is very versatile and has been used for the

electrocatalytic oxidation of alkenes,69'70 ketones,68-70 aldehydes,68'71 sugars72'73 and









DNA.72,74,75 A simplistic view of the catalytic cycle is shown in Scheme 1-6. In this

cartoon a potential capable of oxidizing the metal center from Ru(II) to Ru(IV) is applied

at the electrode. The Ru complex is first oxidized at the electrode surface before reacting

in solution with the substrate regenerating the Ru(II) aquo complex.


[ (trpy)(bpy)RuVO ]2+ Substrate
(Ox)




2H
2e- Substrate
[ (trpy)(bpy)Ru"(OH2) ]2+ +
H20
Electrode Bulk
Surface Solution

Scheme 1-6. Adapted from reference 76.

Since Meyer's publication65 in 1980 on the electrocatalytic properties of

[(trpy)(bpy)RuIV(O)]2+, the catalytic abilities of several other polypyridyl complexes have

been reported. An example of this is [Ru(4,4'-Me2bpy)2(PPh3)(H20)][(C104)2], an active

electrocatalyst that selectively oxidizes primary alcohols to the corresponding aldehyde.77

Cyclic voltammograms of these solutions exhibit an increase in anodic current when an

alcohol is introduced. This increase in current is characteristic of the catalytic

electrooxidation of alcohols by RuV=0.78

Extensive mechanistic studies have been performed on the electrooxidation of

aqueous alcoholic solutions with ruthenium complexes. Several mechanisms have since

been proposed with each containing a Ru-oxo complex as the catalytically active species.

The Ru-oxo bond is either generated in situ from water or is present beforehand in the










pre-catalyst. The mechanisms which have been proposed are hydride transfer79'80

(Scheme 1-7), oxygen insertion81 (Scheme 1-8) and hydrogen atom abstraction82 (Scheme

1-9).

2+
2+ CH CH3 + H3 rapid 2+ CH3
1 1 -0 1I1
Ru"=o] +HC-OH Ru-O--H--C-OH Ru-OH + COH+ Ru-OH2 + C=O
I CH CH
CH3 CH, CH3 CH3


Scheme 1-7. Adapted from reference 79.

2+
H
[ RuVI(trpy)(0)2(CH3CN) ]2+ (trpy)(CH3CN)(O)Ru=O /OH
+ ---
PhCH2OH H Ph



2+

H OH

(trpy)(CH3CN)(O)RuIV O-C-Ph [RuIV(trpy)(0)(CH3CN)2 2++ PhCH(OH)
H




PhCH(OH)2 PhCHO + H20

Scheme 1-8 Adapted from reference 81.

rapid
RuIV=02+ + PhCH20H RunI-OH2+ + PhCHOH rap RuI-OH22++ PhCHO

Scheme 1-9 Adapted from reference 82.

Reactivity of Bimetallic Complexes

The term "catalysis" was coined by Berzelius in 1836 to describe a new force other

than affinity that can drive a reaction to completion. The modern definition of a catalyst

is any substance that accelerates the rate of a chemical reaction without being consumed

during the reaction. From an economical and environmental standpoint, catalytic









reactions currently dominate the chemical industry.83 These reactions have a

considerable impact on the production of pharmaceuticals, agrochemicals, polymers, fine

chemicals, etc.84 Catalysis offers the possibility of achieving complex synthetic

transformations with high efficiency, chemical and stereochemical control while

minimizing, if not eliminating, waste products and solvents.

Because of the distinct advantages gained from being able to catalyze chemical

reactions, researchers are constantly trying to improve upon the reactivity and selectivity

of current catalysts. It is clear that the catalytic reactions that occur in nature are

generally far superior to the reactions developed by chemists. The elucidation of many

enzymatic processes has revealed the interaction of two or more reactive centers during

some of these catalytic transformations. The multifunctional catalysis observed in nature

is rarely exploited in synthetic catalysts which chiefly utilize a single reactive site.

In trying to mimic the hydrolytic cleavage of a phosphate ester bond by a

metalloenzyme, Reinhoudt developed 1 a calix[4]arene functionalized with two Zn(II)

metal centers. Complex 1 catalyzes the cyclization of the RNA model substrate

2-(hydroxypropyl)-p-nitrophenyl phosphate85 (HPNP, Scheme 1-10) with a 23,000 fold

rate increase at pH 7 and 25 C. The increased activity of 1 was explained via a

bifunctional mechanism (Scheme 1-10) in which one zinc center acts as a Lewis acid and

activates the phosphate group while the second activates the nucleophilic hydroxyl group.

Bimetallic complexes are now an accepted means to improving the catalytic

properties of some mononuclear systems.8789 In recent years heterobimetallic complexes

have also received a tremendous amount of attention due to the possibility of exploiting

the different reactivities of the metal centers during a chemical reaction. An example














1 I






W x
-N0






R CHa2c2OEt

Scheme 1-10. Adapted from reference 86.

relevant to this dissertation is the Oppenauer-type oxidation of primary and secondary

alcohols to the corresponding aldehyde and ketone with complex 2 (Table 1-1).90

Although the mechanism for this catalytic cycle is not entirely clear, it is apparent that

both metal fragments are crucial to the performance of the catalyst. This certainty was

based on the two key observations made by Severin:

1. Under similar conditions, Ru and Rh homobimetallic complexes displayed
no Oppenauer-type oxidative ability (Table 1-1)

2. Ligand modification to the Ru or Rh fragment affects the activity of the
complexes

Another example relevant to this dissertation is the heterobimetallic catalyst

[N(n-Bu4)][M(N)R2(t-O)2CrO2] where M= Ru or Os developed by Shapley.6'91 When air

is used as the co-oxidant, this complex selectively oxidizes benzylic, primary and

secondary alcohols at 60 OC to the corresponding carbonyl compounds. A mechanism

based on the experimental results is shown in Scheme 1-11. It was proposed that after

coordinating to Os there is a proton transfer to one of the bridging oxo ligands, followed










by P-hydride elimination and formation of the carbonyl compound. After the carbonyl

compound dissociates, molecular oxygen is activated by the Os-Cr bond, regenerating the

starting metal complex.6

Table 1-1. Catalytic oxidation of 1-phenylethanol. Adapted from reference 90.
RT, 6H
OH 0.2 mol % catalyst 0
1 eq. K2CO3
Acetone
~~llJ


Heterobimetallic Electrooxidation Catalysts

Previous studies in the McElwee-White research group resulted in the synthesis of

three heterobimetallic complexes CpRu(PPh3)([t-C1)(Ct-dppm)PtCl2 (3),

CpRu(PPh3)(t-C1)(t-dppm)PdCl2 (4) and CpRu(PPh3)(C1)(t-dppm)AuCl (5).92,93

Complexes 3 5 were prepared by reacting CpRu(PPh3)(Cl)(rl-dppm) (6) with

Pt(COD)C12, Pd(COD)C12 or Au(PPh3)Cl (Scheme 1-12) at room temperature. The

molecular structures of 3 5 were confirmed via X-ray crystallography and NMR.


Catalyst Conversion /%

Ph3P /C Ph Ph
Ph u R'


2

RPh R P
0 -R< Cl h Rh <94



Ph Ph Ph Ph

Ph3P /CI Cl
P .PRu i Ru I PPh3
Ph3P Cl PPh3 <
A04 3










N
Os"O O
R
^


N
RwOsPO O
R O CO
R ~)iLb


N

Os O
R Cr
1 O


- H20, PhCHO
.0f ______


N


lH HO
H" ~
0o


N
iiil 0

0--0
s O //


Scheme 1-11. Adapted from reference 6.


Pd(COD)C12


Ru./Cl
Ph3P /RC
Ph2P--PPh2
6


Au(PPh3)C1


Cl

RP u Pd
Ph3P/ I cl
Ph2P-PPh2
4



Ru\ /l
Ph3P /Au
Ph2P PPh2


Scheme 1-12.


6









Cyclic voltammetry (CV) of complexes 3 5 was performed in 1,2-dichloroethane

(DCE) containing 0.7 M tetrabutyl ammonium trifluoromethane sulfonate (TBAT). All

three complexes exhibited three oxidation waves (Table 1-2). The first and third wave

are assigned to the Ru(IIIII) and Ru(IIIIV) couples respectively, while the middle wave

is assigned to the redox couple of the second metal.

Table 1-2. Formal potentials for complexes 3, 4, 5 and 7
Complex Couple E1/2 (V) Couple Epa (V) Couple Epa (V)

Ru/Pt (3) Ru/ 1.21 PtII/IV 1.69 RuIII/IV 1.91

Ru/Pd (4) Ru"1/"' 1.30 PdI/ 1.49 Ru"IIV 1.92

Ru/Au (5) Ru"/1' 0.89 Au/ 1.42 RuIIIIV 1.81

CpRu(l2-dppm)C1 (7) Ru/' 0.61 RuIII/IV 1.38
a All potentials obtained in 0.7 M TBAT / DCE and reported vs NHE. Adapted from
reference 92.

Cyclic voltammetry was also used in screening the electrocatalytic properties of

CpRu(PPh3)(p-C1)(p-dppm)PtCl2 (3), CpRu(PPh3)(p-C1)(p-dppm)PdCl2 (4) and

CpRu(PPh3)(C1)(p-dppm)AuCl (5) towards methanol oxidation. For complex 3, the

introduction of methanol (Figure 1-2) results in a significant increase in current that

coincides with the Pt(II/IV) redox wave. This increase in current is typical of an

electrocatalytic oxidation process, and is also observed at the Pd(II/IV) redox couple of

complex 4. In contrast, the catalytic current of the Ru/Au complex does not occur at the

Au(I/III) couple but at the Ru(III/IV) couple.

Product Formation

As previously described, the surface catalyzed electrooxidation of methanol

involves a complicated multistep reaction (Eq. 1.6 1.12). When the electrooxidation of

methanol is performed with a homogeneous catalyst, the oxidation products are









400
- 10 mM Catalyst -

300 + 0.35 M MeOH
S- + 5 pLH2 /
200 /




I I I I I
100





0 0.5 1.0 1.5 2.0 2.5

Potential / V vs NHE


Figure 1-2. Cyclic voltammograms of 3 under nitrogen in 3.5 mL of DCE/0.7 M TBAT;
glassy carbon working electrode; Ag/Ag reference electrode; 50 mV/s
solutions as specified. Adapted from reference 93.

formaldehyde (Eq 1.15) and formic acid (Eq 1.16). In the presence of excess methanol

both formaldehyde and formic acid undergo condensation reactions to form

dimethoxymethane (Eq. 1.17) and methyl format (Eq. 1.18) respectively. It is important

to point out that with the excess of methanol present the equilibria for these reactions

should favor the formation of DMM and MF. Therefore when observed, DMM is formed

from the incomplete 2e- oxidation of methanol. MF is formed from the 4e- oxidation of

methanol. Current efficiency was calculated based on the yields of DMM, MF and the

total charge passed (Eq 1.21).


96485 (C mol-1) 1 (.
efficiency charge passe ) 2DMM(mol) + [ 4 xMF(mol) x 100(%) (1.21)
efcecy charge passed (C)l









Bulk Electrolysis of Methanol

The bulk electrolyses of 3 5 and the Ru model compound CpRu( 2-dppm)C1 (7) were

performed at 1.7 V, the potential at which the catalytic current begins for complex 3.

Oxidation with the Ru/Pd complex 4 was performed between the Pd(II/IV) and

Ru(III/IV) waves, while electrolysis with the Ru/Au compound 5 was performed between

the Au(I/III) and Ru(III/IV) waves. Oxidation of methanol with the Ru model compound

7 was performed at a potential more positive than the Ru(III/IV) couple.

The organic products of bulk electrolyses of dry methanol were analyzed with a gas

chromatograph (GC) and identified as dimethoxymethane and methyl format. The

formation of these products is consistent with the electrooxidation of methanol on Pt/Ru

electrodes. A result of this condensation reaction is that water is formed during the

electrolysis. Addition of water not only results in an increase in the catalytic currents for

compounds 3 5 (Figure 1-2) but also favors the formation of methyl format

(Table 1-3).

Table 1-3. Bulk electrolysis data for the oxidation of methanol by 3 7
Dry Current Dry Wet Current Wet
Complex Efficiencyb Product Ratiob Efficiencyb Product Ratiob
(% ) (DMM/MF) (% ) (DMM/MF)
3 18.6 1.20 19.5 0.41
4 24.6 0.87 20.6 0.54
5 25.4 0.46 26.1 0.34
7 3.2 co 7.2 0.33
a Electrolyses were performed at 1.7 V vs NHE. b Product ratio and current efficiencies
after 130 C of charge passed. Adapted from reference 92.

Current efficiencies for the oxidation of methanol with 3 5 and 7 are summarized

in Table 1-3. Although the current efficiencies of the heterobimetallic complexes are

moderate at best (18 26 %), they are still significantly higher than that of the Ru model

compound (3 7 %). These results indicate that there is a cooperative interaction









between Ru and the second metal center resulting in an enhancement of the catalytic

properties of the heterobimetallic complexes relative to their mononuclear components.

Summary

Ruthenium complexes have been studied as alcohol electrooxidation catalysts since

the 1970s. Heterobimetallic homogeneous electrocatalysts is a fairly new field, with

research being driven by the McElwee-White group. As a result of this research it is

evident that the non-Ru metal center of 3 5 has a profound effect on the catalytic

activity of the heterobimetallic complexes. The remainder of this dissertation will focus

on the role of the non-Ru metal center during the electrooxidation of methanol with

ruthenium heterobimetallic complexes.














CHAPTER 2
SYNTHESIS AND ELECTROCHEMICAL PROPERTIES OF A
RUTHENIUM / MERCURY HETEROBIMETALLIC COMPLEX

Introduction

Interest in heterobimetallic complexes has grown significantly in the last twenty

years, mainly due to the potential catalytic application of interacting metal centers.9497

Cooperative interaction between metal centers has been shown to generate catalysts with

greater reactivity and selectivity than their mononuclear components.98-100 A similar

cooperative effect was observed during the electrooxidation of methanol on Pt/Ru binary

anodes. A cooperative effect was also observed during the oxidation of alcohols with

Ru/Rh (Table 1-1) and Os/Cr (Scheme 1-11) homogeneous catalysts. Interest in this

cooperative effect led to the synthesis, and investigation of the electrocatalytic properties

of CpRu(PPh3)([-C1)(C-dppm)PtCl2 (3), CpRu(PPh3)([-C1)(t-dppm)PdCl2 (4) and

CpRu(PPh3)(C1)([-dppm)AuCl (5).92,93 Complexes 3 5 were used as catalyst during the

electrooxidation of methanol and resulted in significantly better current efficiencies

(Table 1-2) than the mononuclear model complex CpRu(r2-dppm)C1.92

The increased activity displayed by complexes 3 5 during the methanol oxidation

reaction inspired further study and led to the synthesis of 8 14. In complexes 8 14 the

structures of 3 5 were altered by varying the ligands.101 The CVs of 8 14 (Table 2-1)

are similar to those observed for 3 5, and the assignment of the redox waves were made

from comparison to these complexes. Electronic interaction between the metal centers of

complexes 8 12 is observed in their CVs. The presence of a bridging halide promotes










"Cl1
Ru Pt
Ph3P/ I Cl
Ph2P- PPh2

3


S I

Ru Pt
Ph3P/ I Cl
Ph2P_ PPh2

8


Ru Pt
Ph3P/ I
Ph2P PPh2

9


I Cl
/\C1i
Ri Pd
Ph3P/ I C1
Ph2P. PPh2

4



Ru PId
Ph3P" I Cl
Ph2P- PPh2

11


Cl Cl
Ru Pd
Ph3P I CH3
Ph2P, PPh2

12


R,,C1 Cl
Ru /
Ph3P' k /Au
Ph2P- PPh2

5


SI I
Ru /
Ph3P' /Au
Ph2P- PPh2

13



R &Cl Cl
Ru /
Ph3P' /Au
Ph2P. ,PPh2

14
14


l.Cl

Ru Pt
Ph3P/ ICH3
Ph2P PPh2

10

Figure 2-1. Structure of compounds 3 5 and 8 14

this interaction, and the donation of electron density from Ru to Pd or Pt is reflected in

the Ru(II/III) oxidation potential. Due to the considerable loss of electron density, the

Ru(I1IIII) oxidation wave for complexes 8 12 occurs at a much higher potential than

CpRu(PPh3)(Cl)(rl-dppm) (Table 2-1). The lack of electronic interactionbetween the Ru









and Au metal centers can also be observed by examining the CV data (Table 2-1). The

Ru(II/III) and Au(I/III) oxidation waves of 13 and 14 are shifted only slightly relative to

their monometallic model compounds.

Table 2-1 Formal notentials for comnlexes 8 14


A ll otetiilas tULainIIe in U. / II IDTAI / ICE andIL dIUepotLe Vs INIE. iAUaptLeU Iulo
reference 101.

The electrooxidation of methanol was performed with complexes 8 14 at 1.7 V in

0.7 M TBAT / DCE, forming DMM and MF (Table 2-2) as the only oxidation products.

By expanding the Ru/M series of complexes, it is apparent that the Ru/Au complexes are

less active during this reaction, than the Ru/Pd and Ru/Pt complexes (Table 2-2). In fact

the current efficiency of the Ru/Au complexes are more comparable to the Ru model

compound CpRu(PPh3)2C1 than to the Ru/Pt and Ru/Pd complexes.


Complex Couple E1/2 (V) Couple Epa (V) Couple Epa (V)

8 Ru" "1 1.25 Pt I 1.54 RuIIIV 1.90

9 Ru1/1 1.10 Pt/V 1.49 Ru/V 1.98

10 Ru1'111 1.08 Pt /V 1.53 Ru/' 1.95

11 Ru"/11 1.29 Pd/V 1.55 Ru/V 1.98

12 Ru"/11 1.10 Pd/V 1.50 Ru/V 1.95

13 Ru1/1 0.89 Au/1 1.54 Ru/V 1.80

14 Ru111 0.75 Au11 Ru- 1.76

CpRu(PPh3)(Cl)(T 1-dppm) (6) Ru" "11 0.72

CpRu(PPh3)2C1 Ru" "I/ 0.87
a A11 ,*--,-*j. k ,,1'7 f Am in A r. -A 'xTThT A A*\A C .--.









Role of the Non-Ru Metal Center

From the current efficiencies in Table 2-2 it is evident that the non-Ru metal center

is critical to the improved catalytic ability exhibited by the heterobimetallic complexes.

Possible roles of the non-Ru metal include:

* Oxidant
* Activation of the Ru metal center
* Methanol binding site

Table 2-2. Bulk electrolysis data for the oxidation of methanol by 8 14
Cop a Current Efficiency Product Ratio
Cmplx (%) (DMM / MF)
3b 18.6 1.20

8 43 0.98

9 39 1.26

10 32 3.02

4b 24.6 0.87

11 42 0.91

12 23 2.94

5b 25.4 0.46

13 16 2.10

14 12 2.32

CpRu(PPh3)2C1 12 2.87

CpRu(r2-dppm)Cl 3.2 o
a Electrolyses performed at 1.7 V vs NHE. Product ratio and current efficiencies after
130 C of charge passed. Adapted from reference 92. b Adapted from reference 101.










The oxidation of alcohols by Pt,102 Pd103-106 and Au107 complexes have literature

precedent and are still being actively investigated. Recent examples of these

transformations with molecular oxygen as the co-oxidant are shown in Schemes 2-1 and

2-2.

OH O

Pd(OAc)2 (5.0 mol%)
Pyridine (20 mol%)
+ 1/2 02-------*
+ 1/22 molecular sieves, + H20
toluene, 80 C

Scheme 2-1. Adapted from reference 105

AuCl (5.0 mol%)
OH Ligand (6.3 mol%) O
Conversion 100 %
Toluene, 90 oC, air Yield 99 %



Ar, ,Ar
Ne N
Ligand


Scheme 2-2. Adapted from reference 107.

The Pt, Pd or Au center could also activate the Ru by mediating the electron

density around it. The mediation of the Ru(II/III) couple of complexes 8 12 (Table 2-1)

is an example of this. The bridging halide of complexes 8 12 facilitates the electronic

interaction between Ru and Pt or Pd. As a result of this interaction the Ru metal center of

complexes 8 12 will be more electrophilic than complex 6. The increased

electrophilicity (Lewis acidity) of Ru would then favor the interaction / coordination with

the nucleophilic methanol substrate.

The third possibility that exists is a site for methanol binding. In this role the Pt, Pd

or Au metal center would bind and activate the methanol before oxidation is performed










by the Ru metal center. A similar bifunctional mechanism4446 was proposed for the

oxidation of methanol by PtRu binary anodes in DMFCs.

The second and third roles are closely related and could possibly be performed by a

Lewis acid metal center. To investigate the role of the second metal a Ru/Hg complex

similar to the Ru/Pt and Ru/Pd complexes (Figure 2-1) was synthesized. Mercury was

selected because it is of moderate Lewis acidity and non-redox active within the potential

window used.

Lewis Acid Catalysts

Lewis defined an acid in 1923 as an electron pair acceptor while a Lewis base is an

electron pair donor. The term "Lewis acid" is now used to differentiate this interaction

from the Bronsted-Lowry acid (proton donor). Lewis acid catalyzed reactions have a rich

history in organic synthesis and continue to be extensively studied (Figure 2-2).





1111111


81111









21111



1975 1980 1985 1990 1995 2000 2005
Year


Figure 2-2. References to "Lewis acid" in the scientific literature (SciFinder Scholar).









Carbon-carbon bond formation via the Friedel-Crafts reaction (Eq. 2.1), Mukaiyama

aldol synthesis, the Diels-Alder and ene reactions are classic organic reactions catalyzed

by conventional Lewis acids such as AlC13, SnC14 or TiC14.108 These simple Lewis acids,

although very moisture sensitive, are capable of catalyzing a large number of reactions

but with limited stereo-, regio- and chemo- selectivity.

H3C CH3
CHCH3

+ H3C Cl -- + HC1

CH3 (2.1)




In this modem age of organic synthesis, selectivity is as important a factor to the

viability of a catalyst, as is its reactivity. Due to continuing research in the field of Lewis

acid catalyzed reactions, two key goals have been met.

1 The number of metals widely used in Lewis acid reagents has grown significantly.
Currently more than 28 metals are used in Lewis acid catalyzed reactions each
with its own attributes. The expansion of the Lewis acid reagents has led to
reactivity previously unavailable to conventional Lewis acids (Eq 2.2).109

0 0


OEt 0 0
+ 10 % Yb(OTf)3
12 % TMEDA

|| H20, 25 C, 16 h


71% (2.2)










2 Design of novel ligands capable of stabilizing and promoting unique reactivity of
Lewis acid metal centers. An example of this is the enantioselective Diels-Alder
reaction (Eq. 2.3) reported by Kelly110 in 1986. In this reaction the C2 symmetric
ligand (a derivative of binaphthol) leads to one enantiomer being favored.


Ph

OH

OH

Ph

2 equiv


1) BH3
AcOH

2)
2) 11


OMe


70 90 % yield
> 98 % ee


OH 0 OMe (2.3)

With the use of non-traditional Lewis acids and the design of some novel ligands, the

limitations of conventional Lewis acids have been to a large part surmounted. It is now

possible to do Lewis acid catalyzed reactions under less stringent conditions, with high

stereo-, regio- and chemo- selectivity.

Classification of Lewis Acids

Even though a large number of metal reagents have been used as Lewis acids

during catalytic organic transformations, most of these reagents are chosen only after

experimental trial and error. Trial and error is necessary because scientists currently only









have a crude understanding of Lewis acidic character. There have been a few attempts at

classifying Lewis acidic reagents. These classifications have been made using one of the

following methods:

* Reactivity of a Lewis acid
* NMR data
* Theoretical calculations

In 1972 Olah arranged over 130 Lewis acids based on their activity during a

Friedel-Crafts reaction (Scheme 2-3).111 The Lewis acids were then placed in one of four

categories: very active, moderately active, weak or very weak (Scheme 2-3) based on the

amount of products formed during the benzylation and subsequent isomerization.

CH3

CH2C1
Very active
+ Lewis acid H Lewis acid Isomerization
SH2C Products

CH3


Lewis Acid Classification
Very active: High conversion, large amount of isomerization products = A1C13, GaCl3, NbC15, TaC15

Moderately active: High conversion, very little isomerization = InC13, WC16, ReCl5, SbCl5

Weak: Low yield, no isomerization = SnCl4, BBr3, TiCl4, FeCl2, PtCl4

Very weak: No Products = SbCl3, BeC12, CuC12, IrCl3, HgC12, AuCl3

Scheme 2-3. Adapted from reference 111.

Kobayashi grouped Lewis acids based on the activity and selectivity during the

addition reaction of a silyl enolate to an aldehyde and an aldimine (Scheme 2-4).112

Based on the experimental results the Lewis acids were classified as: active, weak or

inactive (Scheme 2-4).









OH 0

Ph Ph Ph A
0 Ph Me3SiO
S + MC1+
A & --ph
Ph H Ph H Ph NH 0

Ph )Ph B

Lewis Acid Classification
Active: Yields greater than 40 % = AC13, GaCl3, NbCl5, TaCl5
Weak: Yields less than 40 % = FeCl2, PtCl2, RuC13, SiCl4
Inactive: No Products = HgC1, HgCl2,PdCl2, AuCl

Scheme 2-4. Adapted from reference 112.

Lewis Acidic Properties of Mercury Complexes

In both classification schemes by Olah111 and Kobayashi112 the mercury halides

HgCl and HgC12 are listed as inactive and therefore are very weak Lewis acids. As with

most metal complexes, the Lewis acidity of mercury is greatly affected by the ligands

coordinated to it. Experiments designed at tuning the Lewis acidity through ligand

variation have been performed with mercury organometallic complexes.113116 The aim of

these experiments is to investigate the mechanism by which polyfunctional Lewis acids

activate carbonyl groups during organic reactions. It has been proposed that chelation of

the carbonyl group by Lewis acids plays an important role in the enhanced catalytic

activity. The Lewis acidity of mercury halides can be increased by coordinating with an

electron withdrawing ligand (Scheme 2-5).113 Complex 15 exhibits strong Lewis acidic

character readily forming an adduct with acetone. The bidentate coordination was

confirmed with a crystal structure of the solvent adduct.









H3C CH3


C Cl O Cl
Cl g \ ,, /
Hg Hg Hg

acetone

F F F F


F F F F

15

Scheme 2-5.

The Lewis acidity of the Hg metal center can be increased even more by expanding the

fluorinated backbone. This strategy led to the isolation of the trimeric perfluoro-ortho-

phenylene mercury complex (Figure 2-3).115 This complex has a strong affinity for

aromatic compounds and has formed isolable 1:1 adducts with biphenyl, naphthalene,

pyrene and triphenylene. The 7t stacking of trimeric perfluoro-ortho-phenylene mercury

and aromatic hydrocarbons result in phosphorescence being observed for the aromatic

substrate. It is thought that the phosphorescence is due to a heavy atom effect of mercury

promoting intersystem spin crossing from the Si to the T1 state.115

F F F

F- / Hg-\ /F


Figure 2-3. Structure of trimeric perfluoro-ortho-phenylene mercury









Chemistry of Mercury

Organometallic chemistry effectively started in 1849 when Frankland observed that

metallic zinc reacts with methyl iodide. Frankland later extended this reaction to other

metals and prepared several new organometallic compounds, one of which was

methylmercuric iodide. During characterization of methylmercuric iodide he recorded

the nauseous taste, totally unaware of its extraordinary toxicity. Mercury compounds are

extremely toxic and exposure can occur through inhalation, ingestion or dermal

absorption. The amount of mercury absorbed by the body is dependent upon the

chemical form. Only 0.01 % of elemental mercury is absorbed when ingested but methyl

mercury is almost totally absorbed. In the human body mercury accumulates in the liver,

kidney, blood and brain. Due to decreased handling of mercury acute health effects such

as cardiovascular collapse or kidney failure (both of which are fatal) are not as common

today. Chronic health effects include central nervous system effects, kidney damage and

birth defects. Genetic damage is also suspected. Due to the high toxicity of mercury it

cannot be overstated how important it is to follow proper lab procedures when handling

any material containing this element.

Mercury Catalyzed Reactions

There are limited examples in the literature for mercury catalyzed reactions. A

recent example of this includes the reaction between alkynes and phosphonic acid

monoesters (Eq. 2.4) to yield vinyl phosphonates.117

O O
I OEt 10mol% Hg(OAc)2 IIOEt
RCI= CH + R2Pt -P- Ri ,,o R
R CH + RP 2 mol % BF3.OEt2 R R2
toluene, 80 C
Yields = 50- 90 % (2.4)









Mercury acetate is essential to the reaction, forming the corresponding Markovnikov

adducts in moderate to good yields with high regioselectivity. Little to no vinyl

phosphonates were formed when other addition catalysts such as RuC13, PdCl2(PPh3)2

and Pd(PPh3)4 were used.

Another Hg(II) catalyzed reaction is the homogeneous oxidation of methane to

methanol (Eq. 2.5 2.8).11 This transformation is extremely selective (85 %) with high

yields (43 %) in the presence of Hg(II) ions.

HgS04
CH4 + 2 H2S04 -Hg CH30SO3H + 2 H20 + SO2 (2.5)

CH30SO3H + H2O -CH30H + H2S04 (2.6)

S02 + 1/2 02 + H20 H2S4 (2.7)

CH4 + 1/202 0 CH3OH (2.8)

Synthesis and Characterization of CpRu(PPh3)(p-C1)(p-dppm)HgCl2

Attempted Synthesis of CpRu(PPh3)(p-C1)(p-dppm)HgCl2 (16)

Initial attempts at preparing 16 involved reacting CpRu(PPh3)Cl(rl-dppm) with

HgC12. A similar method was used during the synthesis of complexes 3 5 (Scheme 1-

12) and for the preparation of (CO)3Ru(at-Ph2PCH2NC4HsO)2HgI2 (Eq. 2.9).119 Instead

of the desired dppm bridged complex the reaction between CpRu(PPh3)Cl(r1-dppm) (6)

and HgCl2 led to the formation of [CpRu(PPh3)(r2-dppm)] (17) (Eq 2.10) as confirmed

by 31P {H} NMR (Table 2-3). The phosphorus NMR of 17 displayed a triplet at 50.2

ppm for the Ru bound PPh3 and a doublet at 2.2 ppm for the chelated dppm. ZnCl2 and

CdC12 also reacted in a similar manner and an unrefined X-ray crystal structure of the

resulting Zn complex can be seen in Figure 2-4.










p N

\CO
OC-Rii


P N


HgI2


p N

\CO
OC-Ru Hgl2
*CO
P N


P N O




+


R .,X
Ru
PhP/ PP
Ph2P3 PPh2
PhzP h2


MC12
M = Zn2+, Cd2+, Hg2+

X = C1-, I-


3 / PPh2
Ph2P








PH5

S PH7


PH3


Zn2
C12 CI3


Figure 2-4. Unrefined crystal structure of [CpRu(PPh3)(r2-dppm)] [ZnC13]- (17).


(2.9)


MC12X]


(2.10)









Synthesis of CpRu(PPh3)(p-C1)(p-dppm)HgCl2 (16)

An alternative route to 16 was found by first reacting CpRu(PPh3)Cl(rq-dppm) (6)

with Hg(OAc)2 followed by acetyl chloride (Eq. 2.11). CpRu(PPh3)([t-Cl)([t-

dppm)HgCl2 is a yellow air and moisture stable solid. Solutions of 16 are also very

stable when stored in an inert atmosphere; they however decompose upon prolonged

exposed to air. The 31P{ 1H} NMR spectrum of complex 16 displays the expected

resonances (Table 2-3). The Ru bound phosphorus signals appear as a doublet for PPh3

at 40.0 ppm (Jpp= 41 Hz) and a doublet of doublets for dppm at 35.1 ppm (Jpp = 41 Hz

and 11 Hz). The Hg bound phosphorus appears as a doublet at 29.7 ppm (Jpp = 11 Hz).


S,\\C1,,- /A CH3COCI Ru I cHg
1 Hg(OAc)2 HgAc P / I
Ph3P/ Ph3P OAc
Ph3 2 PPh2 h Ph2p PPh2 Ph2PhPPh2

6 18 16 (2.11)

Synthesis of CpRu(PPh3)(p-C1)(p-dppm)Hg(OAc)2 (18)

The Hg acetate intermediate CpRu(PPh3)([t-C1)(tC-dppm)Hg(OAc)2 (18) that is

formed during the synthesis of 16 (Eq. 2.11), can be isolated cleanly and in high yields if

acetyl chloride is not added to the reaction mixture. The stability of complex 18 is very

similar to 16, and it is isolated as an air and moisture stable yellow solid with moderate

stability in solution. Complex 18 displays the expected 31P{ H} NMR spectrum, which is

analogous to that of compound 16 (Table 2-3). The Ru bound phosphorus signals are

shifted downfield relative to the analogous signals in 16, appearing as a doublet for PPh3

at 41.9 ppm (Jpp = 43 Hz) and a doublet of doublets for dppm at 36.9 ppm (Jpp = 43 Hz









and 28 Hz). The Hg bound phosphorus signal is shifted upfield relative to 16, appearing

as a doublet at 24.1 ppm (Jpp = 28 Hz).

Table 2-3. Selected NMR data for complexes 16 18
Complex Ru-PPh3 Ru-dppm Hg-dppm
16 39.9 (d, Jpp = 40 Hz) 35.0 (dd, Jpp = 40, 10 Hz) 30.1 (d, Jpp = 10 Hz)
17 48.0 (t, Jpp = 35 Hz) 1.9 (d, Jpp = 35 Hz)
18 41.9 (d, Jpp =43 Hz) 36.9 (dd, Jpp = 43, 28 Hz) 24.1 (d, Jpp = 28 Hz)

Analysis of CpRu(PPh3)(p-Cl)(p-dppm)HgCl2 Structure

Selected bond lengths and angles for 16 are shown in Table 2-4; crystallographic

data and structure refinement are provided in Table 2-5. In the solid state, the crystal

structure of CpRu(PPh3)([-C1)(t-dppm)HgCl2 contains the complex and two disordered

DCE solvent molecules with no unusual contacts between any of these species. Complex

16 (Figure 2-5) contains a bridging chloride and dppm moiety as do the structurally

similar CpRu(PPh3)([-C1)(C-dppm)PtCl2 (3) and CpRu(PPh3)([-C1)(t-dppm)PdCl2 (4).

The metal centers and bridging ligands form a distorted six-membered ring consisting of

Ru, C13, Hg, P1, C6 and P2.

The Cp ligand is bound to Ru in a r15 mode resulting in the typical three legged

piano stool conformation about the Ru center. The Ru-Cl bond length of 2.4577(8) A in

16 is longer than distance of 2.4403(7) A reported for the Ru-Cl bond in complex 4. The

Ru-Cl bond in 16 is comparable to that of complex 5, [2.4598(11) A] whose chloride is

not bridging. The Hg metal center is four coordinate and forms bonds with three

chlorides and a phosphorus atom to give the expected tetrahedral geometry. The Hg-C13

bond length of 2.7372(8) A is shorter than the bridging chloride [2.763(9) A] reported for

the Hg dimer [Hg2(C1)2([t-C1)(lt-dppm)2] in which the Hg centers are also bridged by

two dppm ligands. The bridging chloride exerts a strong trans effect on the Hg-Cll bond








[2.4901(11) A] making it much longer than the Hg-C12 bond [2.3993(9) A]. The bond
lengths of both terminal chlorides are shorter than the terminal Hg-Cl bonds reported for

Rh2Cp2(tC-CO)(t-dppm)(t-HgCl2) [2.534(3) A and 2.581(3) A] and within the typical
range of four coordinate Hg species (2.28 2.68 A).


I


Figure 2-5. Thermal ellipsoids drawing of the molecular structure of
CpRu(PPh3)([t-C1)(tC-dppm)HgCl2 (16). Thermal ellipsoids are plotted at
50 % probability. Phenyl rings and hydrogen atoms are omitted for clarity.
Table 2-4. Selected bond distances (A) and angles (deg) for
CpRu(PPh3)([t-C1)(tC-dppm)HgCl2 (16).
Bond Length ( A) Bond Angle ( deg)
Hg-P1 2.4143(8) P1-Hg-C13 90.44(2)
Hg-Cll 2.4901(11) P1-Hg-Cll 111.24(4)
Hg-C12 2.3993(9) Cll-Hg-C13 102.94(4)
Hg-C13 2.7372(8) C13-Hg-C12 104.67(3)
Ru-P2 2.3193(8) Cll-Hg-C12 102.66(5)
Ru-P3 2.3387(8) Hg-C13-Ru 110.87(3)
Ru-C13 2.4577(8) P2-Ru-C13 92.69(3)
Ru-C1 2.217(3) P3-Ru-C13 88.32(3)
Ru-C2 2.230(3) P1-C6-P2 117.71(16)
Ru-C3 2.232(3)
Ru-C4 2.186(3)
Ru-C5 2.178(3)









Table 2-5. Crystal data and structure refinement for
CpRu(PPh3)(u-C1)(p-dppm)HgCl2 (16)
Formula C52H5oCl7HgP3Ru
Formula weight 1317.64
Temperature 193(2) K
Wavelength 0.71073 A
Crystal system Monoclinic
Space group Cc
Unit cell dimensions a =23.384(2) A
b =11.5264(7) A
c 19.295(2) A
Volume (A3) 5182.2(6)


a =900
P= 94.875(2)
y =900


Density (calcd) (Mg/m3)
Absorption coefficient (mm-1)
Fooo
Crystal size (mm3)
o range (deg)
Index ranges
Reflections collected
Independent reflections
Completeness to theta = 27.500
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I >2sigma(I)]

R indices (all data)
Absolute structure parameter
Largest diff. peak and hole (e.A3)


1.689
3.739
2600
0.27 x 0.23 x 0.20
1.75 to 27.50
-30 22341
11134[R(int)= 0.0160]
99.1%
Analytical
0.5328 and 0.3680
Full matrix least squares on F2
11134 / 2 / 581
1.023
aR1 = 0.0207

aR1 = 0.0211
-0.0063(17)
0.893 and -0.607


aRl = (||IFo| Fcl|) / Y|Fol, bwR2 = [[w(Fo2 Fc2)2] / YwfFo]2]1/2, S = [Y[w(Fo2 Fc2)2]
/ (n-p)]1/2w= /[C2(Fo2)+( 0.027*p)2+8.56*p], p = [max(Fo2,0)+ 2* Fc2]/3

Cyclic Voltammetry

The first three ionization potentials for mercury are 10.43, 18.65 and 34.4 eV

respectively. The large difference between the second and third ionization potentials is

one reason why the formation of Hg(III) species is so difficult if not impossible to attain.

There is only one report of a Hg(III) species, a short lived [Hg(cyclam)]3+ which was

electrochemically generated and observed in 1976.120 Unfortunately, this experiment has


bwR2 = 0.0523
[10968]
bwR2= 0.526









never been independently confirmed. Based on this and the absence of any oxidation

waves for the model compound HgC12(PPh3)2 (0 2.0 V), it was assumed that Hg(II) is

non-redox active within the potential window used for these studies.

During the CV studies of complex 16, three irreversible redox waves at 0.70, 1.02 and

1.50 V were observed (Figure 2-6). Three oxidation waves were unexpected since the

only redox active species in the solution is the Ru(II) metal center. During previous

studies on complexes 3 14 (Table 1-1 and Table 2-1) only two Ru based redox

processes, the Ru(II/III) and Ru(III/IV) oxidation waves were observed. Since Hg(II) is

not redox active within the potential window used in these experiments there should only

be two oxidation processes. With subsequent scans the first and third wave diminish in

intensity, until only the second oxidation wave, now shifted to 1.14 V (Figure 2-6) was

observed. Analysis of the resulting solution after the CV experiments confirmed that

CpRu(PPh3)(t-C1)(t-dppm)HgCl2 (16) had decomposed during the CV experiments.

The decomposition of 16 resulted in the formation of [CpRu(PPh3)(r2-dppm)] (17). A

comparison of the CVs for [CpRu(PPh3)( 2-dppm)]+[PF6]- and 16 after decomposition

allowed the assignment of the oxidation wave at 1.14 V (Figure 2-6) to the Ru(II/III)

couple of [CpRu(PPh3)( 2-dppm)]+. The first oxidation wave at 0.70 V is much lower

than any observed for the halide bridged complexes 8 -12 (Table 2-1). The oxidation

wave at 0.70 V is instead closer to the Ru(II/III) couple of CpRu(PPh3)(Cl)(rl-dppm) (6)

and CpRu(PPh3)(Cl)(p-dppb)AuCl (14) (Table 2-1), complexes containing no halide

bridge. The stability of 16, in 0.7 M TBAT / DCE was monitored via 31P{ 1H} NMR.

Complete decomposition to 17 occurred after only 5 hours, without the passage of any

current. A similar result was observed at lower electrolyte concentration















140


120 ,,,
R If Hg9
Initial Scan php/ I
10 Ph2 p PPh2



Ph, P PPh2
100 o 1 ,-'



80
60
After Decomposition /


40




0


-20
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2

Potential / V vs. NHE





Figure 2-6. Cyclic voltammograms of 16 under nitrogen in 3.5 mL of DCE / 0.7 M
TBAT; glassy carbon working electrode; Ag/Ag reference electrode; 50
mV/s scan rate.

(0.1 M TBAT / DCE). The supporting electrolyte was also changed to the weakly


coordinating electrolyte tetra-n-butylammonium tetrakis(pentafluorophenyl)borate.


Changing the supporting electrolyte had no effect, and CpRu(PPh3)([t-C1)(tC-dppm)HgCl2


(16) still decomposed to [CpRu(PPh3)(r2-dppm)] (17). These results indicate that the


decomposition is not only due to the passage of current but also to the interaction of the


supporting electrolyte with the complex.


Summary

A novel Ru/Hg complex CpRu(PPh3)([t-C1)(tL-dppm)HgCl2 (16) was synthesized


and characterized. The metal centers are connected with a bridging chloride and dppm






42


ligands. This is the first reported Ru/Hg complex bridged in this manner.

CpRu(PPh3)(t-C1)(t-dppm)HgCl2 is unstable in solutions containing electrolyte, and

rapidly decomposes to [CpRu(PPh3)(r2-dppm)] (17) during cyclic voltammetry. Due to

the instability of 16 during the CV experiments, the electrocatalytic properties of

CpRu(PPh3)(t-Cl)(t-dppm)HgCl2 were not studied














CHAPTER 3
THE SELECTIVE PARTIAL ELECTROOXIDATION OF METHANOL TO
DIMETHOXYMETHANE WITH RUTHENIUM/TIN HETEROBIMETALLIC
COMPLEXES

Introduction

The cooperative interaction between Ru/Pt, Ru/Pd and Ru/Au complexes has been

shown to improve the catalytic ability of the heterobimetallic complexes relative to the

monometallic components.92,121 As mentioned before one possible role of the non-Ru

metal center could be as a Lewis acid. To continue the study of this interaction, a series

of Ru/Sn complexes was synthesized and characterized.

Chemistry of Tin

As a group 14 element, tin has the ability to form stable and relatively strong bonds

with most elements in the periodic table.122 Except for the bonds formed to the heavier

alkali and alkaline earth metals, most of the bonds formed to tin are covalent in character.

The first and second ionization potentials for tin are similar to those of elements that

readily form divalent cations (Table 3-1). Hence it is not surprising that tin is able to

form stable Sn(II) compounds. The more stable oxidation state is Sn(IV), but the energy

difference between it and Sn(II) is very small (Eq 3.1). Due to the stability of the two

Sn2+ i Sn4+ + 2 e- E = 0.1364 V (3.1)

oxidation states, there are extensive and varied chemistries for both states. Kinetically

stable trivalent complexes have been isolated but generally Sn(III) is considered unstable

and is thought to readily disproportionate.









Table 3-1. Selected ionization potentials
Ionization Potential (eV)
Element 1st 2nd 3rd 4th
C 11.260 24.383 47.887 64.492
Sn 7.344 14.632 30.502 40.734
Mg 7.464 15.035
Ca 6.113 11.871
Mn 7.435 15.640
Fe 7.870 16.18

Bonding in Heterobimetallic Tin (II) Complexes

Tin is known to form heterobimetallic complexes containing metal-metal bonds to

transition metals, lanthanides, actinides and group 12 metals. In bonding to transition

metals, stannylenes donate two of the available p electrons to the transition metal.

Stannylenes can also act as Lewis acids, forming adducts with both hard and soft Lewis

bases. These adducts are better Lewis bases than the stannylenes (eg. SnC13I is a better

Lewis base than SnC12). There are empty low lying p and d orbitals on tin, which when

hybridized are capable of accepting electron density from the transition metal. Due to

these factors the bonds between tin and a transition metal contain both a and Rt

components.

Synthesis of Ruthenium / Tin (II) Complexes

There are several synthetic routes available for the preparation of M-Sn complexes,

such as salt elimination, elimination of small molecules, oxidative addition, insertion of

tin (II) and transmetalation. For the group VIII metals (Fe, Ru and Os), the synthesis is

often accomplished via the following methods:

Salt elimination:123 Na2Ru(CO)4 + 2 Ph3SnCl -- (Ph3Sn)2Ru(CO)4 + 2 NaCl (3.2)

Oxidative addition:124 Fe(CO)4(PPh3) + SnC14 (SnCl3)Fe(CO)3(PPh3)Cl + CO (3.3)

Insertion of SnC12:125 CpRu(PPh3)2C1 + SnCl2 -- CpRu(PPh3)2(SnCl3) (3.4)









Mechanistic information on the formation of M-Sn complexes is limited. The

insertion of tin (II) halides however, has been the subject of much discussion. Though

not proven conclusively, there is evidence for the mechanism in Scheme 3-1. It has been

proposed that the tin (II) halide first coordinates to the halide ligand of the transition

metal before rearranging intramolecularly to the three centered intermediate.

SnX2
I
M-Y

/ \, nX2
1 \
LM-Y + SnX2 LnM- Y- SnX2 L %M Y Y LnM-SnX2


Scheme 3-1. Adapted from reference 126.

Evidence to support this mechanism includes the isolation of a bridging halide complex

Ir([-Cl)(SnCl2)(CO)(PPh3)2.127 The reaction between CpRu[Ph2PCH(CH3)CH2PPh2]C1

and SnC12 (Scheme 3-2) also provides evidence for the intramolecular rearrangement,

since the reaction proceeds with retention of configuration at Ru.128 The diastereomers

formed during the reaction are configurationally stable and therefore do not interconvert

as a solid or in solution.

Heterobimetallic Tin (II) Catalysts

Stannylene complexes are often utilized as catalysts or co-catalysts due to the two

following properties:

1. As a ligand, tin exerts a strong trans effect hence facilitating the establishment of
a vacant coordination site on the transition metal.

2. Tin (II) compounds readily undergo oxidative addition and subsequent reductive
elimination.

Heterobimetallic tin complexes have been used in hydrogenation,126'129

dehydrogenation,125'126'130-132 Friedel-Crafts alkylation,133 polymerization134,135 and









hydroformylation.136-138 Of relevance to this dissertation is the thermal dehydrogenation

of methanol by Ru/Sn heterobimetallic catalysts.

Ph Ph Ph Ph

S Ru \ SnC12 H I Ru C
H3CIIC / C H3CI P/ SnCl3
H '//Ph
H /Ph H Ph
Ph

Yield > 98 %


Ph Ph Ph Ph

H2C P\ P C1 SnC12 H2C P\ \\SnC13
Ru I Ru
H3CIIIC / HgCIIC P / C
3 P. Cp H3C P. Cp
H Ph H Ph
Ph Ph

Yield = 90 %

Scheme 3-2. Adapted from reference 128.

A series of Ru/Sn heterobimetallic complexes has been investigated as catalysts for

the thermal dehydrogenation of methanol.132 A comparison of [RuCl2{P(OMe)3}4],

[RuCl(SnCl3){P(OMe)3}4] and [Ru(SnCl3)2{P(OMe)3}3] reveals that the SnCl3- ligand is

vital to the catalytic activity. [Ru(SnCl3)2{P(OMe)3}3] is the only complex that catalyzed

the conversion of methanol to acetic acid or methyl acetate (due to the esterification of

acetic acid). 132

The mechanism for the thermal dehydrogenation of methanol has been studied but

is not yet fully understood.125'130,132'139 Carbonylation was ruled out as a possible route to

methyl acetate since isotopically labeled 13CO was not incorporated into the product. The

reaction path in Scheme 3-3 was then suggested based on previously observed

















CH3CO2H



CH3


C +H

Ln Ru-SnXm


CH30H

Slow


H2CO


LnRu -


- H


H2
C -0
Ln Ru I
O-CH2


CH3
Ln Ru
O-C-H
II


reductive
pliminatiom


H CH3 V

O HCO2CH3


Ln Ru-SnXm LnRu

Scheme 3-3. Adapted from reference 139.

transformations. Dehydrogenation of methanol to formaldehyde is known to occur for

Ru complexes.140 It has also been reported that H2CO can react with metals to give a

methyl-formato complex which upon reductive elimination yields methyl formate.141 It is

then suggested by Shinoda that methyl format (which is observed in the reaction

mixture) is isomerized to acetic acid.139 The isomerization is thought to go through a four

center interaction (Scheme 3-3) which is favored by the soft and hard nature of Ru(II)

and Sn(II) respectively. The methyl migration step is not evident, but would be stabilized









by the resulting acetate bridge. Other evidence to support methyl migration is that ethyl

and isopropyl formates also react to form propionic and isobutyric acids (or their esters)

respectively.132

The Ru/Sn complexes investigated as catalysts for the dehydrogenation of

methanol include CpRuP2X where X = SnF3, SnC13 and SnBr3 and P2 = PPh3, PPh2Me

and dppe.125 These catalysts were very selective during the dehydrogenation of

methanol, forming only methyl acetate. For these catalysts Gusevskaya suggested that

the Lewis acidic tin halide ligand rendered Ru more electrophilic. The increased

electrophilicity of Ru will favor the P-hydride interaction and subsequent elimination

(Eq 3.5) proposed as the rate determining step (Scheme 3-3).

Cp
I Cp
.-', SnCl3 slow H-RI -SnCl3
H OH-R
\/ t

/ \H O CH
H H
H (3.5)

Methanol as a Chemical Feedstock

Due to the ease of transportation, storage and reactivity, methanol has been utilized

as a chemical feedstock in several industrial processes. Examples of these include the

carbonylation of methanol to acetic acid, a chemical reagent used in the production of

polymers, aspirin and solvents. The Monsanto process,142 commercialized in 1970, is

based on the use of homogeneous Rh catalysts, while the Cativa process,143

commercialized in 1996, uses Ir catalysts. Combined, both catalytic cycles account for

approximately 80 % of the acetic acid produced worldwide.143









Another industrial example is the methanol to olefin or methanol to gasoline

process patented in 1975 by Mobil. In this reaction methanol is converted to ethylene

(Scheme 3-4) or propylene over solid acid catalysts. The light olefins can then be used to

produce longer chain hydrocarbons. Because of increasing demands for light olefins as a

chemical feedstock, this reaction continues to be an industrially interesting process.

-nH2O
n CH30H -- (CH2)n gasoline

Scheme 3-4. Adapted from reference 144.

The selective oxidation of methanol has also been of interest as a route to several

important organic chemicals such as formaldehyde,145 methyl formate146 (MF) and

dimethoxymethane147-150 (DMM). Due to the low toxicity, good solvent power,

amphiphilic nature, low viscosity, low surface tension and high evaporation rate DMM

has many industrial applications. DMM is utilized as a solvent in the cosmetic,

pharmaceutical and paint industries as well as a chain length regulator during the

preparation of ion exchange resins. Another recent application of DMM is that of an

additive to diesel fuel.

Current Environmental Protection Agency (EPA) regulations require a 95 %

reduction in harmful emissions from diesel engines.151 When fully implemented in 2010

it is estimated that 2.6 million tons of smog-causing nitrogen oxide (NOx) emissions and

110,000 tons of particulate matter (PM) will be reduced each year. It is proposed that

these reductions in smog and particulate matter will have a profound effect on our quality

of life. An estimated 8,300 premature deaths, 5,500 cases of chronic bronchitis and

17,600 cases of acute bronchitis in children will also be prevented annually. It is also

estimated that more than 360,000 asthma attacks and 386,000 cases of respiratory









symptoms in asthmatic children will be avoided every year. In addition, 1.5 million lost

work days, 7,100 hospital visits and 2,400 emergency room visits for asthma will be

prevented. 15

NOx species are generated from nitrogen and oxygen under the high pressure and

temperature conditions in the engine. Diesel PM is a complex aggregate of solid and

liquid material, the formation of which is not exactly understood. Currently pre- and

post-combustion methods are being examined for reducing NOx and PM emissions. One

pre-combustion method uses reformulated diesel fuels containing oxygen rich additives

such as certain alcohols, esters, glycol ethers and carbonates. DMM is one additive that

has been investigated and shown to reduce PM and soot emission from diesel engines.

The commercial synthesis of DMM is performed using a two-step process

involving oxidation of methanol to formaldehyde followed by the condensation of the

methanol/formaldehyde mixtures to yield DMM. Due to increasing demands for DMM

the direct conversion of methanol1147150 to DMM has been recently investigated as a

possible replacement for the two step process. Rhenium oxides147'148 and heteropolyacids

with Keggin structures149'150 have been reported to catalyze the selective oxidation of

methanol vapor to DMM, typically at temperatures above 400K. Among these catalysts,

SbRe206147'148 has the highest selectivity for DMM, converting 6.5 % of the methanol

feed at 573K with a selectivity as high as 92.5 %.

Electrooxidation of methanol typically yields a complex mixture of products

(Scheme 3-5), with the major product and selectivity dependent upon the reaction

conditions.153-156 Product distributions have been determined in conjunction with studies

on direct methanol fuel cells,22,30'153'155-160 using Pt black,153'157'158 Pt/Ru157'158 and









Pt/Nafion (Pt-SPE)155,156,159 anodes. The general trend is that the absence of water and

lower methanol concentrations favor formaldehyde formation, with yields of DMM rising

as the concentration of methanol increases. The presence of water favors formation of

MF and/or complete oxidation to CO2.

-2e, -2H+ -2e-, -2H+ -2e, -2H+

CH30H H2CO HCOOH CO2
H20

+2 CH3OH + CH30H


H2C(OCH3)2 + H20 HCOOCH3 + H20

Scheme 3-5. Adapted from reference 152.

Electrochemical Synthesis of Organic Molecules

Electrochemistry is a powerful technique capable of performing versatile and

unique organic transformations. During electrochemical reactions, organic substrates can

be activated by adding (reducing) or removing (oxidizing) electrons. The result of this

process is the generation of radical anions or cations. Since these electrons are generated

from the electrode, there is no reagent waste. Because of this electroorganic synthesis is

often considered environmentally friendly.

The advantages of this technique are:

The selectivity of the reaction can be influenced by the applied potential
Reaction rate is influenced by the current density
Reaction conditions are typically very mild
Environmentally friendly, no need for chemical oxidizing or reducing
agents

Disadvantages associated with electroorganic synthesis include:

Special reactors and equipment, fortunately most of these are now
commercially available









Electron transfer is a heterogeneous process, therefore electrodes with
large surface area must be used so as to accelerate the reaction rate
Recovery of supporting electrolyte is often difficult and can be expensive

The first notable application of electrochemistry to organic synthesis was reported

in 1843 by Kolbe.161 During this reaction carboxylic acids are decarboxylated to give an

acyloxy radical intermediate that rapidly dimerizes to form a hydrocarbon. Yields for

Kolbe type electrolysis typically range from 50 90 %, remarkably high for a reaction

generating an alkyl radical. Since the work of Kolbe was published, research into

electrochemical synthetic transformations has been extensively studied. As a result of

these studies some interesting reactions have been developed. Selected examples are

shown in Eq. 3.6 3.9.162 It should be pointed out that the fluorination and reduction

reactions (Eq 3.7 and 3.8) are unique to electrosynthesis.

H2 H2 PbO2 anode
HO-C -C-C-C -OH HOOC-C-C-COOH
Oxidation: H2SO4, H20 (3.6)

HF
CH3-(CH2)n- SO2C1 CF3-(CF2)n- SO2F
Fluorination: Ni anode (3.7)

NO2 NHOH NH2

Cu cathode rearrangement

H20, H2S04 6 -L

Reduction: OH (3.8)


Pb cathode

SH20, H2S04 N
Hvdrogenati on H (3 9)


--~ -- -~---------


.











Electrosynthesis of organic compounds is not limited to only laboratory scale

preparations, but is also widely used for industrial applications. One example is the

reduction of acrylonitrile to adiponitrile (Eq. 3.10), a chemical feedstock used in the

synthesis of nylon. The actual reaction is very complicated, involving parallel pathways

and competing products. The major side reactions can be limited, to yield adiponitrile

selectively (90 %).

2 CH2=CHCN + 2 H20 + 2 e NC(CH2)4CN + 2 OH- (3.10)

Table 3-2. TEMPO mediated electrooxidation of carbohydrates


Substrate3 Pro duct Yield (%)

HO COOH
o 0


OH OH 96
OCH OOHH




0H 0H
OH OH

HO COOH

0 0

OH O LCHI OH 89
OH OH



OH OH
HO CO OH
0 0





-n n



a Electrolyses performed at 0.53 V vs SCE. Adapted from reference 163.









Apart from the direct electrochemical processes described above indirect

electrochemical transformations are also used during the synthesis of organic compounds.

An example relevant to this dissertation is the selective oxidation of carbohydrates with

2,2,6,6-tetramethylpiperidin- 1-oxyl (TEMPO) (Table 3-2).163 Secondary hydroxyl

groups are in most cases inert during the electrolysis. This selectivity allows the

oxidation of carbohydrates to the corresponding carboxylic acids in moderate to excellent

yields. The catalytically active species is the nitrosonium ion formed after the one-

electron oxidation of TEMPO (Scheme 3-6). The mechanism proposed for the




-( N
1 e-

RCH2OH
Electrode /


pH > 3 0. RCHO


N RCOOH
O N
OH

Scheme 3-6. Adapted from reference 163.

electrooxidation of carbohydrates, is the same mechanism proposed by de Nooy164 for the

oxidation of alcohols under basic conditions. The initial step is the coordination of the

alkoxy to the nitroso group. After 3-hydride elimination the corresponding aldehyde is

formed, the hydrate of which can be further oxidized to the carboxylic acid.









The electrochemical oxidation of organic molecules with TEMPO is of interest for

industrial applications because:

1. TEMPO and its derivatives are cheap and easily prepared
2. TEMPO is easily recovered in quantitative yields after oxidation of
polysaccharides
3. As an oxidant TEMPO is very selective
4. Reaction work up is easily performed


In 2002 and 2003 the McElwee-White group reported that Ru/Pt, Ru/Pd and Ru/Au

heterobimetallic complexes can act as catalysts during the electrochemical oxidation of

methanol.92'93'101 For these complexes the non-Ru metal center was shown to improve the

catalytic properties as compared to the mononuclear model compounds

CpRu(q2-dppm)C1 and CpRu(PPh3)2C1. Related beneficial effects of a Lewis acidic tin

center in a thermal reaction had previously been reported for CpRu(PPh3)2(SnCl3) (20),

which selectively oxidizes methanol to methyl acetate at elevated temperatures.125,165

In order to continue the study of Lewis acidic interactions during the

electrochemical oxidation of methanol the catalytic properties of Ru/Sn complexes 19 -

26 (Figure 3-1) were studied. This chapter also describes the selective partial oxidation

of methanol to dimethoxymethane using the Ru/Sn complexes CpRu(PPh3)2(SnCl3) (20),

(Ind)Ru(PPh3)2(SnCl3) (21) and CpRu(TPPMS)2(SnCl3) (23).

Synthesis

Synthesis of CpRu(TPPMS)2CI (22)

The literature procedure for the synthesis of CpRu(TPPMS)2C1166 yielded a

complex reaction mixture in which unreacted triphenylphosphine monosulfonate

(TPPMS) and TPPMS oxide were the only identifiable compounds. Samples of 22 were

instead prepared by an alternate route involving substitution of PPh3 in CpRu(PPh3)2C1









(19) with TPPMS (Eq 3.11). The reaction of TPPMS with a slight excess of

CpRu(PPh3)2C1 was performed in refluxing toluene. Complex 22 was isolated in

excellent yields (90 %) as an orange, moderately air stable solid. The 31P {H} NMR

spectrum of CpRu(TPPMS)2C1 is very similar to that of CpRu(PPh3)2C1, consisting of a

singlet at 40 ppm.


Ru
Ph3P \\R X
PPh3


(19)

(20)


Rut
Ph3P\' ~ SnC13
PPh3


Cl

SnCl3


(21)






I


(24)

(25)

(26)


(22) X = Cl

(23) X = SnCl3

Figure 3-1. Structure of compounds 19 26


n =1, dppm

n = 2, dppe

n = 3, dppp











.Ru
N= Toluene phe' Cl1
+ 1.8 TPPMS Ph2\
Ph3P R ''/ 48 hours, Reflux PPh2
PPh3 N 0
Na -03S
SO3- Na

19 22 (3.11)






Synthesis of CpRu(TPPMS)2(SnC13) (23)

The Ru/Sn complex CpRu(TPPMS)2(SnCl3) was prepared in an analogous manner

to CpRu(PPh3)2(SnCl3)125 by reacting 22 with a slight excess of SnC12 (Eq. 3.12) in

ethanol. The insertion of Sn into the Ru-Cl bond is facile and the reaction is complete

after one hour. The resulting bright yellow solid is moderately stable in air and in

solutions of methanol and acetonitrile, but decomposes rapidly when dissolved in water.

As expected from the NMR spectrum of CpRu(PPh3)2(SnCl3),125 the 31P{ H} NMR

spectrum of CpRu(TPPMS)2(SnCl3) consists of a singlet at 46 ppm with 2Jp-sn = 422 Hz.



EtOH Ru
p.P RuC1 +1.2 SnC12 Ph2hp\\-' SnC13
Ph2P 24 hours, RT PPh2


Na -3S Ph Na -03S 00
SO3 Na S03


22 23 (3.12)

Before the synthesis of CpRu(TPPMS)2C1 (22) and CpRu(TPPMS)2(SnCl3) (23) all

electrochemical experiments in the McElwee-White lab were performed in the









chlorinated solvents CH2C12 or DCE. CH2C12 or DCE had to be used because of the

organic nature of the ligands used in complexes 3 5 and 8 14. These solvents have a

low dielectric constant, and therefore a high ohmic resistance. Because of the resistance,

a high concentration of supporting electrolyte has to be used in order to get a reasonable

conductivity and electron transfer rate. In order to improve the electron transfer

properties of the reactions being studied there has been a concerted effort to use more

polar solvents such as methanol and water. As a result of this CpRu(TPPMS)2C1 (22) and

CpRu(TPPMS)2(SnCl3) (23) have been synthesized. Another reason for performing the

electrochemical studies in water is to be able to compare these catalysts to the widely

studied [(trpy)(bpy)Ru"(OH2)]2+. As mentioned before the aquo ligand plays a crucial

role in the catalytic cycle of [(trpy)(bpy)Ru"(OH2)]2+, being deprotonated (Eq. 1.19 and

1.20) to form the catalytically active oxidant [(trpy)(bpy)Ru'V()]2+

Synthesis of CpRu(q2-dppm)(SnC13) (24)

Complex 24 was prepared in an analogous manner to CpRu(T2-dppe)(SnC13) in

high yields (85 %), by reacting CpRu(12-dppm)C1 with SnC12 (Eq. 3.13). The 31P {H}

NMR spectrum consists of a singlet at 8.3 ppm with tin satellites (2Jpsn = 385 Hz). This

singlet is shifted upfield by approximately 6 ppm relative to CpRu({2-dppm)C1. The 1H

NMR spectrum exhibits a shift downfield for the methylene and cyclopentadienyl protons

of approximately 0.3 ppm.



EtOH
,,,+ 1.1 SnCl2 Ru
Ph2P R + 11 1 5 hours, Reflux Ph R ""/SnC13
PPh2 PhPPh
pph2 PPh2


24 (3.13)









Synthesis of CpRu(q2-dppp)(SnC13) (26)

CpRu(q2-dppp)(SnC13) (26) was prepared in an analogous manner to

CpRu(q2-dppe)(SnC13) in high yields (85 %), by reacting CpRu(q2-dppm)Cl with SnC12

(Eq. 3.14). The 31P{ H} NMR spectrum consists of a singlet at 33.9 ppm, shifted upfield

by approximately 5 ppm relative to CpRu(q2-dppp)C1. Complex 26 has a low solubility

in the NMR solvents used; because of this no tin satellites were observed. The 1H NMR

spectrum exhibits a shift downfield of approximately 0.4 ppm for the cyclopentadienyl

protons. A similar shift downfield was observed for CpRu(q2-dppm)(SnC13) (24).



EtOH
Ru1,. +1.1SnC12 R u "/SnC'
Ph2P i'i"C 5 hours, Reflux Ph2P Sn13
PPh PPh2


26 (3.14)

The Ru/Sn complexes CpRu(PPh3)2(SnCl3) (20), (Ind)Ru(PPh3)2(SnCl3) (21) and

CpRu(TPPMS)2(SnCl3) (23) are coordinatively saturated. Before the methanol oxidation

reaction can occur, there has to be ligand dissociation and methanol coordination.

Phosphine dissociation has been invoked in numerous mechanisms, and it is this reason

why phosphine ligands are often used in metal catalysts. Gusevskaya proposed that

phosphine dissociation is a key step during the thermal dehydrogenation of methanol with

CpRu(PPh3)2(SnCl3) (20). To probe if a vacant coordination site on Ru is needed, a

series of Ru/Sn complexes containing the bidentate phosphines dppm, dppe and dppp was

synthesized. If phosphine dissociation occurs during the catalysis the chelate effect of the









bidentate phosphines should result in a decrease in the reaction rate of 24 26 relative to

20.

NMR Data
1H and 31P { H} NMR spectroscopies were utilized to determine the ligand

arrangement about the Ru center. Selected NMR data are presented in Table 3-3. Only

one singlet is observed in the 31P{ H} NMR spectra of these complexes suggesting that

the phosphine ligands are in similar chemical environments. The proton NMR spectra of

the complexes exhibit characteristic peaks for the phenyl, indenyl and cyclopentadienyl

groups.

The electron density at the Ru metal center can be varied by changing the

peripheral ligands. The chemical shifts of the cyclopentadienyl protons were predictable

based on the Lewis acidity of the additional ligands. When the Lewis acidity of the

ligands is increased, the Ru metal center will become electron poor and the Cp protons

will become deshielded. By being deshielded the Cp protons now experience more of the

applied magnetic field and shift to a higher frequency. Hence for CpRu(PPh3)2(X) the Cp

resonance of X = SnC13 (4.54 ppm) > Cl (4.10 ppm)

Table 3-3. Selected NMR data for complexes 19 26


Cp 31P {H}
Complex Solvent H NMR NMR 2Jp,sn
(ppm) (ppm) (Hz)
CpRu(PPh3)2C1 (19) CDC13 4.10 39.9
CpRu(PPh3)2(SnCl3) (20) CDC13 4.54 45.2 435
(Ind)Ru(PPh3)2(SnCl3) (21) CDC13 48.8 363
CpRu(TPPMS)2C1 (22) DMSO-d6 4.07 40.1
CpRu(TPPMS)2(SnCl3) (23) CD3OD 4.65 46.0 422
CpRu(r2-dppm)(SnC13) (24) CDC13 5.08 8.3 385
CpRu( 2-dppe)(SnCl3) (25) CDC13 4.89 77.5 397
CpRu(r2-dppp)(SnC13) (26) CDC13 4.84 33.9
a 1b) 2 1 1 -


All NMR data obtained at room temper
observed.


_-^.11:^._









Cyclic Voltammetry

Since Sn(II) is not redox active within the solvent window of these experiments, it

is assumed that any observed redox processes would be due to oxidation of the Ru metal

center. Cyclic voltammograms of complexes 19 26 in solutions of methanol (0.50 to

1.40 V) or DCE (0.50 to 1.60 V) each display a single oxidation wave in the potential

range of the experiments. This oxidation process has previously been assigned for the

monometallic complexes CpRu(PPh3)2C1167 and (Ind)Ru(PPh3)2C1168 (Table 3-4) as the

reversible one-electron oxidation of the Ru metal center. Based on this assignment the

oxidation waves observed for complexes 19 26 have been assigned to the Ru(II/III)

couple.

Table 3-4. Formal potentials of complexes 19 26
Complex pa(V) El/2b (V) AEp (mV) ipa / ipc
CpRu(PPh3)2C1 (19) 0.87 0.82 90 1.03
CpRu(PPh3)2(SnCl3) (20) 1.48 1.44 85 0.92
(Ind)Ru(PPh3)2(SnCl3) (21) 1.39 1.34 106 0.95
CpRu(TPPMS)2C1 (22) 0.93 0.89 104 1.06
CpRu(TPPMS)2C1 (22)c 0.79 0.73 90 0.94
CpRu(TPPMS)2(SnCl3) (23) 1.58
CpRu(TPPMS)2(SnCl3) (23)c 1.29
CpRu(Q2-dppm)(SnC13) (24) 1.54
CpRu({2-dppe)(SnCl3) (25) 1.53
CpRu(f2-dppp)(SnCl3) (26)d 1.52
CpRu(PPh3)2C1e 0.929 0.869 120 1.00
(Ind)Ru(PPh3)2Clt 0.69 66
a All potentials obtained in 0.7 M TBAT / DCE unless otherwise specified.
b E1/2 reported for reversible waves. Potential obtained in 0.1 M TBAT/MeOH.
d Potential obtained in 0.7 M TBAT/CH2C12. e Reference 167, potential originally
reported vs SCE. fReference 168, potential originally reported vs SCE.

When analyzed in DCE, the one-electron oxidation of CpRu(PPh3)2C1 (Figure 3-2)

at 0.82 V and CpRu(TPPMS)2C1 at 0.89 V are chemically reversible with ipa / ipc 1

(Table 3-4). When small amounts of methanol are added to the DCE solutions, no










significant change is observed in the cyclic voltammograms of 19 and 22 at potentials

less than 1.60 V.


40 5 mM CpRu(PPh3)2Cl
1 + 0.35 M MeOH
+ 5 pL HzO

20



20



20



-40
0.5 0.7 0.9 1.1 1.3 1.5 1.7
Potential / V vs NHE


Figure 3-2. Cyclic voltammograms of 19 under nitrogen in 3.5 mL of DCE / 0.7 M
TBAT; glassy carbon working electrode; Ag/Ag reference electrode; 50
mV/s scan rate, solutions as specified in figure. Adapted from reference 169.

The CV of CpRu(PPh3)2(SnCl3) (20) in DCE exhibits a reversible Ru(II/III) couple at

1.44 V (Figure 3-3). The Ru(II/III) couple is shifted by approximately 600 mV positive

with respect to the corresponding Ru(II/III) wave of CpRu(PPh3)2C1 (19). This positive

shift is consistent with the electron withdrawing SnC13- ligand rendering the Ru in

complex 20 electron-poor relative to that of complex 19. Sn(II) is not redox active within

the solvent window (-0.50 2.5 V vs. NHE) for these experiments. In the presence of

methanol, there is a significant increase in the current that coincides with the oxidation of

the Ru metal center (Figure 3-3). This effect is indicative of an electrocatalytic oxidation

process.










100

80 5 mM CpRu(PPh3)2(SnCI,)
+ 0.35 M MeOH
60 -- + 5 pL H20'/
60 ..

40

20 ,
20


20 "'...

-40
0.5 0.7 0.9 1.1 1.3 1.5 1.7

Potential / V vs NHE


Figure 3-3. Cyclic voltammograms of 20 under nitrogen in 3.5 mL of DCE / 0.7 M
TBAT; glassy carbon working electrode; Ag/Ag reference electrode; 50
mV/s scan rate, solutions as specified in figure. Adapted from reference 169.

The CV of 21 is very similar to that of complex 20, exhibiting a reversible

Ru(II/III) couple in DCE (Table 3-4). The Ru(II/III) couple however, at 1.34 V is 100

mV negative with respect to the analogous Ru(II/III) couple of complex 20. This shifting

of the II/III couple168 is due to additional electron density associated with the indenyl

ligand. The current rise from electrooxidation of methanol by 21 also coincides with its

Ru(II/III) redox wave, as evidenced by a increase in the current at 1.34 V in the presence

of methanol.

The CV of 23 exhibits a single irreversible wave in DCE at 1.58 V (Table 3-4).

This irreversible redox wave has been assigned to the oxidation of the metal center from

Ru(II) to Ru(III). The single irreversible Ru(II/III) wave is also observed in methanol at

1.29 V, shifted by approximately 290 mV relative to the redox potential in DCE. Cyclic

voltammetry of 23 in DCE exhibits a significant increase in the catalytic current at the









Ru(II/III) wave when methanol is introduced. A similar catalytic effect was observed for

20 and 21.

Methylene chloride solutions of CpRu(T2-dppm)(SnC13) (24),

CpRu(q2-dppe)(SnC13) (25) and CpRu(q2-dppp)(SnC13) (26) each exhibit a single

irreversible oxidation wave at 1.54, 1.53 and 1.52 V respectively. When methanol is

introduced the expected catalytic current is observed at the Ru(II/III) oxidation wave.

The oxidation waves for 24, 25 and 26 (Table 3-4) are only 20 mV apart. This indicates

that the structurally similar complexes also have similar electronic configuration.

Electrochemical Oxidation of Methanol

The cyclic voltammograms of the Ru-SnC13 complexes all exhibit a significant

current increase in the presence of methanol. As mentioned before, this increase in

anodic current in the presence of an alcohol is characteristic of the catalytic

electrooxidation of alcohols. The onset of this electrocatalytic current for the

heterobimetallic complexes coincides with the oxidation of the metal center from Ru(II)

to Ru(III). A similar current increase was observed in the CVs of the dppm bridged

complexes CpRu(PPh3)(t-C1)(t-dppm)PtCl2 (3), CpRu(PPh3)(t-C1)(t-dppm)PdCl2 (4)

and CpRu(PPh3)(C1)(t-dppm)AuCl (5) when methanol was introduced. For complexes 3

and 4 the increase in the anodic current coincides with the oxidation of the Pt and Pd

metal center. For the Ru/Au complex the onset of the catalytic current coincides with the

Ru(III/IV) redox wave. In contrast to the CVs for the heterobimetallic complexes above,

the CV of the Ru model compound CpRu(PPh3)2C1 (19) (Figure 3-2) exhibits no

significant current increase when methanol is introduced.

In order to assess the electrocatalytic ability of the Ru-SnCl3 complexes, the

electrochemical oxidation of methanol was performed at 1.7 V in 0.7 M TBAT / DCE









(Table 3-5). The anodic potential of 1.7 V was chosen during the catalytic studies of 3,

and is the potential at which the catalytic current begins for complex 3. For comparison

purposes initial catalytic studies of 19 21 and 24 26 were performed at 1.7 V. At 1.7

V, the Ru in all complexes studied will be in the +3 oxidation state and within the

catalytic current region.

Bulk electrolysis data for the oxidation of methanol with CpRu(PPh3)2C1 (19),

CpRu(PPh3)2(SnCl3) (20), (Ind)Ru(PPh3)2(SnCl3) (21), CpRu({2-dppm)(SnC13) (22),

CpRu(Q2-dppe)(SnC13) (23) and CpRu(Q2-dppp)(SnC13) (24) are presented in Table 3-5.

Differences between the activities of the complexes can be seen in the turnover numbers,

current efficiencies and product ratios. The chelating phosphines significantly inhibited

the catalytic activity of the complexes. At an anodic potential of 1.7 V,

CpRu(T2-dppm)(SnC13) (22), CpRu(l2-dppe)(SnC13) (23) and CpRu({2-dppp)(SnC13) (24)

exhibited little to no activity for the methanol oxidation reaction. The heterobimetallic

complexes 22 24 are less active than the Ru model compound CpRu(PPh3)2C1 (19).

The Ru model compound CpRu(PPh3)2C1 was more active, forming significantly more

oxidation products. The inactivity of the complexes with bidentate phosphine suggests

that a vacant coordination site on the Ru metal center is critical in the oxidation reaction.









Table 3-5. Bulk electrolysis data for the oxidation of methanol by 19 21 and 24 26
Current Product
a Anodic b DMM MF Ra
Complex TON Efficiency Ratio
Cmple Potential (V) TON Effciency (10moles) (10 moles) (MM/MF)
(%) (DMeM/MF)
CpRu(PPh3)2C1 (19) 1.70 2.60 + 0.15 7.3 + 0.5 6.84 0.34 2.26 0.11 3.0 + 1.0

CpRu(PPh3)2(SnCl3) (20) 1.70 3.37 + 0.20 13.1 + 0.7 8.65 0.43 3.15 + 0.16 2.7 + 1.0

(Ind)Ru(PPh3)2(SnCl3) (21) 1.70 4.69 0.28 17.9 + 1.0 12.1 + 0.60 4.34 0.22 2.8 + 1.0

CpRu(q2-dppm)(SnC13) (24) 1.70 0 0 0 0

CpRu(r2-dppe)(SnC13) (25) 1.70 0.53 0.03 0.78 0.09 1.85 + 0.09 0 oo

CpRu(q2-dppp)(SnC13) (26) 1.70 0 0 0 0

CpRu(PPh3)2C1 (19) 1.55 1.00 + 0.06 5.6 + 0.2 2.69 + 0.13 0.81 + 0.04 3.3 + 1.0

CpRu(PPh3)2(SnCl3) (20) 1.55 3.00 + 0.20 18.2 0.5 9.98 0.50 0.52 0.03 19.2+ 1.1

(Ind)Ru(PPh3)2(SnCl3) (21) 1.55 2.80 + 0.18 16.3 + 0.5 9.07 + 0.45 0.73 0.04 12.4 + 1.1


a All electrolyses performed in 0.7 M TBAT / DCE with 10 mM catalyst, 0.35 M methanol for 5
b Moles of product formed per mole of catalyst. C Calculated using Eq. 1.21.


hours unless otherwise specified.









For the complexes 19 21 with the monodentate phosphines the heterobimetallic

complexes are more active toward methanol oxidation. CpRu(PPh3)2(SnCl3) (20) and

(Ind)Ru(PPh3)2(SnCl3) (21) form greater quantities of oxidation products than the Ru

model compound CpRu(PPh3)2C1 (19). The greater reactivity is also observed in the

current efficiency of these complexes during the reaction. The Ru-SnCl3 complexes have

a higher current efficiency and therefore convert a larger portion of the charge passed into

products.

To probe the effect of the anodic potential on the electrochemical reaction, the

oxidation of methanol with CpRu(PPh3)2Cl (19), CpRu(PPh3)2(SnCl3) (20) and

(Ind)Ru(PPh3)2(SnCl3) (21) was also investigated at 1.55 V (Table 3-5). At 1.55 V, the

Ru metal center in all three catalysts will be in the Ru(III) oxidation state during the

catalysis (Table 3-4). As expected, decreasing the anodic potential has a profound effect

on the amounts of products and the TON (Table 3-5). Significantly less products are

formed at the lower potential when the electrolysis is performed with 19, 20 and 21.

All three complexes CpRu(PPh3)2Cl (19), CpRu(PPh3)2(SnCl3) (20) and

(Ind)Ru(PPh3)2(SnCl3) (21) produce more DMM than MF as evidenced by the large

product ratios (Table 3-5). Reducing the anodic potential has a significant effect on the

selectivity (product ratio) of the reaction when the heterobimetallic complexes are used as

catalysts. For CpRu(PPh3)2(SnCl3) (20) the product ratio increases from 2.07 to 19.2

when the potential is decreased from 1.70 to 1.55 V. A similar effect is observed for

(Ind)Ru(PPh3)2(SnCl3) (21); when the potential is decreased the product ratio is increased

from 2.79 to 12.4. When the Ru model compound is used as the catalyst, the ratio of









DMM:MF is independent of the anodic potential, remaining virtually unchanged when

the potential is decreased.

Bulk electrolyses of the sulfonated complexes 22 and 23 were performed in

methanol as the solvent. The electrolysis in methanol was also studied at two anodic

potentials. Due to the limited anodic range of methanol, the anodic potentials used

during these experiments are 1.40 V and 1.25 V. Similar to the catalysis in DCE and

CH2C12, the electrooxidation of neat methanol resulted in the formation of DMM and

MF. The same trends observed during the electrooxidation of methanol in DCE are also

observed in neat methanol (Table 3-6):

DMM formation is favored over MF, by both complexes

The heterobimetallic complex is much more active than the Ru model
compound

When CpRu(TPPMS)2(SnCl3) is used as the catalyst, lowering the anodic
potential increases the ratio of DMM:MF

When the electrolysis is performed in methanol instead of the less polar DCE or CH2C12,

there is a significant increase in the current efficiency, amounts of products formed and

TON (Table 3-6). This increase in catalytic activity has been attributed to the improved

Table 3-6. Bulk electrolysis data for the oxidation of methanol by 22 and 23
Anodic Current DMM MF Product
Complex Potential TONb Efficiencyc (10-5 (10-5 Ratio
(V) (%) moles) moles) (DMM/MF)
CpRu(TPPMS)2C1 13.4 63.22.3 46.9
(22) 1 0.9 2.34
CpRu(TPPMS)2(SnCl3) 33.4 117
1.25 89.4 + 5.6 5 0
(23) 2.3 5.85
CpRu(TPPMS)2Cl 15.1 9 52.1 + 0.75 6.5
(22) 1.40 1.0 76.9 2.6 2.60 0.04 69.5 1.1
(22) 1.0 2.60 0.04
CpRu(TPPMS)2(SnCl3) 40.0 90.1 6.7 127 + 13.0
(23) _2.6 6.35 0.65
a All electrolyses performed in 0.1 M TBAT / MeOH with 10mM catalyst for 5 hours.
b Moles of product formed per mole of catalyst. C Calculated using Eq. 1.21.









electron transfer kinetics and to the higher concentration of substrate. The

electrooxidation of methanol with CpRu(TPPMS)2C1 (22) and CpRu(TPPMS)2(SnCl3)

(23) at 1.25 V resulted in the selective formation of DMM.

As mentioned before, the electrochemical oxidation of methanol is a complicated

reaction (Scheme 3-5) that often forms multiple stable products (eg. H2CO, HCOOH,

CO, H2C(OCH3)2 and HCOOCH3). To the best of my knowledge this is the first time

that the electrooxidation of methanol resulted in a single oxidation product. When

compared to the high temperature synthesis of DMM (Table 3-7), the electrochemical

oxidation of methanol is a promising alternative for the synthesis of DMM.

Table 3-7. Selective partial oxidation of methanol.
DMM
Reaction D
Catalyst Conditions Selectivity Conversion
Conditions (0/o
(%)
H4PVMo1040 / SiO2a 493 K, 58.1 68
4 kPa CH3OH, 9 kPa 02
SbRe206b 573 K, 92.5 6.5
MeOH/ 02 = 4.0 / 9.7 (mol %)
1.25 V,
CpRu(TPPMS)2C1 (22) 0.1 M TBAT 100 63.2c
0.1 M TBAT / MeOH
1.25 V,
CpRu(TPPMS)2(SnC13) (23) .1 M T T /100 89.4
0.1 M TBAT / MeOH
a Reference 150. b Reference 148. c Current efficiency (Eq. 1.21).

Electrochemical Oxidation of Wet Methanol

The CVs of the heterobimetallic complexes 20 (Figure 3-3), 21 and 23 all display a

slight increase in the catalytic current when small amounts of water are added to the

reaction mixtures. It should be noted that all of the samples contain some water due to

the condensation of methanol with formaldehyde to generate DMM (Scheme 3-5). The

effect of additional water on the electrocatalytic reaction was probed by introducing 5 uL

of water before starting the electrolysis. In DCE the addition of water has a profound









effect on the selectivity of the reaction. The product ratio for the oxidation of "wet"

methanol is lower than the corresponding electrolysis in "dry" methanol (Table 3-8). The

addition of water therefore favors the formation of MF. A similar effect was previously

described for heterogenous148 and similar ruthenium92'93 catalysts.

Table 3-8. Bulk electrolysis data for the oxidation of wet methanol by 20, 21 and 23
Product
Anodic Current DMM MF product
Complex Potential TONb Efficiencyc (10-5 (105 Ratio
(V) (%) moles) moles) (MM
/ MFi
2.50
CpRu(PPh3)2(SnCl3) 1 + 6.45 2.30 2.8
(20) 0.14 0.32 0.11 1.0
0.14
2.90
(Ind)Ru(PPh3)2(SnCl3) 1 .5 20.7 6.67 3.48 + 1.9
(21) 0.16 0.33 0.17 1.0
0.16
CpRu(TPPMS)2(SnCl3) 15.3 42.1 11.5 3.7
d 1.25 74.2 + 3.1
(23)d ____ 5 0.9 74.2 31 2.10 0.57 1.0
a All electrolyses performed in 0.7 M TBAT / DCE with 0.35 M methanol and 5.0 pL
H20 for 5 hours unless otherwise specified. b Moles of product formed per mole of
catalyst. C Calculated using Eq. 1.21. d Electrolyses performed in 0.1 M TBAT/MeOH
with 5.0 tL H20 for 5 hours.

Methyl format formation is also favored in "wet" vs "dry" methanol when the

electrolysis is performed in methanol with CpRu(TPPMS)2(SnCl3) (23). There is

however a significant decrease in the TON and current efficiency of the catalyst

(Table 3-8). During the synthesis of CpRu(TPPMS)2(SnCl3), it was observed that this

complex was very unstable in aqueous solutions. The decrease in TON and current

efficiency is probably due to a shorter catalyst lifetime in aqueous solutions. This

premise is supported by 31P{ H} NMR that revealed more TPPMS oxide in the "wet"

solutions than in the "dry" solutions. CpRu(PPh3)2(SnCl3) and (Ind)Ru(PPh3)2(SnCl3) are

also unstable in solutions containing water. The low solubility of water in DCE probably









accounts for why no significant change in the TON and current efficiency of

CpRu(PPh3)2(SnCl3) and (Ind)Ru(PPh3)2(SnCl3) was observed.

Electrochemical Oxidation of Dimethoxymethane

The electrooxidation of DMM was studied in order to test the competency of DMM

as an intermediate on the pathway to methyl format. Control experiments have

established that the electrooxidation of DMM in DCE does not proceed in the absence of

catalyst at a potential of 1.70 V. The CV of CpRu(PPh3)2(SnCl3) (20) exhibits no

catalytic current in the presence of DMM. After 5 hours of electrolysis at 1.7 V complex

20 formed 6.64 x 10i5 moles of MF with a current efficiency of 14.3 %. These results

indicate that DMM could be an intermediate during the oxidation of methanol to MF

Summary

A series of heterobimetallic complexes containing a Ru-Sn metal bond were

synthesized and characterized. The catalytic activity of these complexes was then

investigated during the electrochemical oxidation of methanol. The catalytic activity of

these complexes is sensitive to the ligands coordinated to ruthenium. Complexes

containing a bidentate phosphine (24 26), display little to no catalytic activity (at an

anodic potential of 1.7 V) during the electrolysis of methanol. This supports the premise

that a vacant coordination site on Ru is critical to the electrooxidation reaction.

Complexes containing a monodentate phosphine (19 23), catalyze the

electrochemical oxidation of methanol to DMM and MF. The Ru/Sn catalysts 20, 21 and

23 favor the formation of DMM; this selectivity can be increased by lowering the anodic

potential. The electrooxidation of methanol is more efficient and selective for the

TPPMS complexes 22 and 23, which allow the oxidation to be performed in methanol.






72


The partial oxidation of methanol to DMM was achieved selectively (100 %) and

efficiently (89.4 %) with CpRu(TPPMS)2(SnCl3) (23).

The addition of water to the DCE and methanol solutions favors the formation of

MF. In methanol, the presence of water increases the decomposition rate of the catalyst.

With a shorter catalyst lifetime there is a significant decrease in the current efficiency and

amount of products when water is added to the methanol solutions. Due to the low

solubility of water in DCE, the catalyst lifetime is not affected by the addition of water to

the DCE solutions.














CHAPTER 4
CHEMICALLY MODIFIED ELECTRODES CONTAINING IMMOBILIZED
RUTHENIUM/TIN HETEROBIMETALLIC COMPLEXES

Introduction

Electrochemistry is a powerful and versatile method for the synthesis of organic

molecules. Transition metals are often used as catalysts / mediators to increase the

reaction rates of these electrochemical reactions. As with most catalytic cycles involving

transition metals, for commercial applications there is a desire to recycle the catalyst.

One method of achieving this is by attaching the catalyst to the electrode surface. These

chemically modified electrodes (CME) have an extensive history, and excellent reviews

on their application have been published.170-172 In this chapter, electrodes modified with

cationic ruthenium complexes will be prepared and studied.

Nafion

Nafion is a fluorinated polymer (Figure 4-1) consisting of a fluorocarbon

backbone and side chains that terminate in an anionic sulfonate site. In the commercially

available membranes, the charge is typically balanced with proton or sodium ions.


[(CF2CF2)n- CF2CF-

OCF2CFOCF2CFSO3-

CF3

Figure 4-1. Structure of Nafion where 5 < n < 7 and m is approximately 1000. Adapted
from reference 173.

Nafion was developed by DuPont in the early 1960s for use in chlor-alkali cells and was

the first ionomer (synthetic polymer with ionic properties) ever synthesized.174 Other









applications of Nafion include as a solid polymer electrolyte in fuel cells and batteries

and a selective drying or humidifying agent for gases. Nafion is also used as a super-

acid catalyst in the production of fine chemicals.

As an ionic derivative of Teflon, Nafion has some unique properties:

Mechanically stable and very resistant to chemical attack.

High working temperatures, stable up to 230 oC.

Ion-conductive, able to function as a cation exchange resin.

Super-acid catalyst, readily donating protons due to the stabilizing effect
of the electron withdrawing fluorinated backbone on the sulfonic acid.

Nafion is very selectively and highly permeable to water. The sulfonic
acid groups in Nafion have a very high water of hydration, so they very
efficiently absorb water.

Extensive research has been performed on the structure of Nafion membranes.175 As a

result of this research Nafion membranes are commonly considered as segregated

domains containing hydrophobic (fluorocarbon) and hydrophilic (hydrated sulfonate)

regions (Figure 4-2). When hydrated the SO3- headgroups are thought to form water

containing clusters approximately 40 A in diameter. These clusters are then connected

within the hydrophobic matrix by short channels 10 A in diameter. It is from this

'inverted micelle' structure that Nafion derives the exceptional ion selectivity and cation

transport properties.

Nafion Supported Metal Catalysts

Because of its stability and cation exchange properties, Nafion has also been

studied as a support for metal catalysts. Supported complexes are formed by covalently

or electrostatically immobilizing metal species into a heterogeneous matrix. Typically

the heterogeneous materials that are used as supports can be placed into three categories:









1. Inorganic matrix containing surface active hydroxyl groups such as A1203
and SiO2
2. Organic polymers containing a pendant ligand such as polystyrene
3. Ion exchange membranes such as Nafion and polyaniline

........ !........ 5.0 W










Figure 4-2. Cluster-network model for hydrated Nafion. Adapted from reference 176.

The concept of immobilizing a soluble metal complex by attaching it to solid

support was first introduced over thirty years ago. Even so this methodology still attracts

considerable interest from the scientific community. The sustained interest in supported

metal complexes is due to the distinct advantages of "heterogenized" complexes over

traditional homogeneous species. Advantages of supported metal complexes include an

increased reactivity and selectivity along with recyclability, stability and an ease of

separation, inherent to heterogeneous systems.

As a result of the advantages listed above, supported metal complexes have been

investigated for possible applications in numerous fields. Of these applications catalysis

has received the most attention, especially for the synthesis of fine chemicals. The first

example of a Nafion supported metal catalyst was published in 1978 by Meidar,177 who

demonstrated that a Hg impregnated Nafion membrane could catalyze the hydration of

alkynes. This catalyst was easily separated from the mixture but upon reuse there was

some loss of activity.177 Since this report there have been several attempts at designing

active Nafion supported metal species as catalysts for organic synthesis.









With properties of an excellent support, a few cationic metal complexes have been

successfully immobilized onto Nafion. In several instances catalytic activities

comparable to homogeneous conditions have been observed for the Nafion supported

catalysts. In 1999 Seen reported the increased catalytic activity exhibited by a Nafion

supported Pd(II) complex during the methoxycarbonylation of ethene.178 Because this

catalyst is limited by diffusion, a combination of low catalyst loading and high dispersion

of Nafion was used in order to increase the activity. When this Nafion supported

catalyst was used in water it was significantly more active than the unsupported catalyst,

having a turnover frequency comparable to commercial applications.

Chemically Modified Electrodes

Chemically modified electrodes (CME) result from the modification of a

conductive substrate to produce an electrode with properties that differ from that of the

unmodified substrate. These electrodes have been studied from the mid-1960s when

French investigated the behavior of a ferrocene modified carbon paste electrode (CPE).179

The composite nature of CPE makes these electrodes among the easiest to modify by

simply admixing a third component with the graphite and binder. Other methods of

preparing modified electrodes include adsorption, covalent attachment and coating the

electrode with multi-layer films. CME are typically designed for applications such as

catalysis or a sensitive sensor. An excellent review on the analytical application of

sensors containing CME was published in 2003.180 Sensor applications of CME are

beyond the scope of this dissertation and will not be reviewed further.

Catalysis can be performed with CME if favorable conditions are present for the

flow of electrons between the electrode and the species to be oxidized or reduced.170

Scheme 4-1 shows a diagram of the reduction of A by the reduced form of the catalyst Q.









The reduction can occur within the film or at the film/solution interface by means of the

reaction paths shown.

A
Q eQ e- A




AA

eQ Q e -A A
e-A

SAA
Q A
e A
e P B B A

Bulk
Electrode Bulk
Surface Film Solution

Scheme 4-1. Adapted from reference 181.

Electrodes Modified with Ruthenium Complexes

CME can be used to catalyze several reactions such as CO reduction, Cr(VI)

reduction, NADH oxidation, the oxidation of small organic molecules such as methanol,

formic acid, propene, ascorbic acid etc. These reactions were recently reviewed by

Malinauskas,182 Andreev183 and Rolison.184 The first example of a ruthenium complex

attached to an electrode is [(bpy)2(H20)Ru(P4VP)n2+] where P4VP is poly-4-

vinylpyridine.64 This ruthenium metallopolymer was covalently attached to the electrode

surface and used as a catalyst during the electrooxidation of isopropanol to acetone. This

complex was not very stable during the catalysis and slowly decomposed to an

unidentified species.









Since the CME containing a ruthenium complex was published, several other

electrodes modified with ruthenium complexes have been prepared.185-189 The methods

of preparation have been varied and include encapsulation of the catalyst into ion-

exchange membranes190-192 such as Nafion and sulfonated polystyrene. Meyer reported

that the dimer [Ru(bpy)2(H20)]204+ in solution is an active catalyst for the

electrooxidation of water.193 When supported on polystyrene sulfonate this complex has

no catalytic activity.194 Meyer proposed that the catalyst deactivation was due to the

displacement of the aquo ligand and formation of a sulfonate complex. The loss of water

will deactivate the catalytic reaction, by inhibiting the formation of the catalytically

active oxo species.

The ruthenium bound CME can also be prepared by attaching the metal complex to

a polymer film.64'187'195'196 The stability of electrodes prepared in this manner has been

studied, and is dependent on the polymer and the method of preparation. In 2000 Meyer

reported that the surface bound poly-cis-[Ru(vbpy)2(0)2]2+ (vbpy is

4-methyl-4'-vinyl-2,2'-bipyridine) is catalytically active during the electrooxidation of

alkyl and aryl alcohols.194 In solution this complex is very unstable readily losing

bipyridine to form the inactive trans-dioxo complex. The rigid nature of the polymer

film retards ligand loss and increases the stability of the catalytically active cis-dioxo

Ru(VI) species.

Preparation of CME

Typically the modified layer is assembled upon a very stable reproducible surface.

This material is normally used as an electrode even when unmodified due to good









mechanical and chemical stability. Examples of typical materials include platinum, gold,

tin oxide and carbon.

As classified by Murray,197 CME can be grouped into four categories based on the

method used to modify them:

Sorption
Covalently modified electrodes
Polymer coatings
Heterogeneous multi-layer

CME prepared using sorption methods rely on chemical and physical interactions to form

and maintain the monolayer.198 These electrodes have the advantage of being easily

prepared but are not as stable as electrodes modified by other methods. Covalent

modification of electrodes is another method for anchoring molecules to an electrode

surface.198 Functional groups which have been employed include >C=O, >C-OH,

-Pt-OH and -Sn-OH. As with the adsorption method, these electrodes are limited to

monolayer coverage, severely restricting the amount of modifier on the surface. The

monolayer limitation can be overcome by preparing multi-layer CMEs. Multi-layer CME

are prepared from uniform polymer coatings of ionomers, redox polymers, inorganic

polymers, polymerization of mediators bearing monomers, etc.198 Another method of

preparing multi-layer CME is the incorporation of mediators in a non-uniform matrix

such as carbon paste, epoxy resin, clay, zeolite and other polymeric systems.198

Electrodes Modified with Bimetallic Complexes

CME have been aggressively studied for the last 20 years (Figure 4-3). The modification

of electrodes with bimetallic complexes however is one field that is still in its infancy,

with only a handful of electrodes studied.192'199-203 The only reference to a







80







31,111,


1111111










51111



1981 -1985 1986-1990 1991 -1995 1996-2000 2001 -2005
Year


Figure 4-3. References to "chemically modified electrodes" in the scientific literature
(SciFinder Scholar).

heterobimetallic complex immobilized on an electrode is the Co(II)-Pt(II) porphyrin

reported by Srour in 2005.204 When adsorbed to the surface of an edge plane graphite

electrode a significant shift (600 mV) in the reduction potential of molecular oxygen was

observed. This CVME can act as a catalyst reducing all of the oxygen present to water

(50 %) and hydrogen peroxide (50 %).

The electrochemical oxidation of methanol with Ru/Sn catalysts in solution was

previously reported from this research group.169 The activity of the Ru/Sn

heterobimetallic catalysts is dependent on the ancillary phosphine ligands. It was shown

that bidentate phosphines greatly inhibited the catalytic activity of the complexes. The

Ru/Sn complexes with monodentate phosphines are very efficient (90 % current

efficiency) and selective (100 % DMM) when the electrooxidation is performed in neat









methanol. In order to continue the study of Ru/Sn Lewis acidic interactions, the synthesis

and study of a series of Nafion supported Ru/Sn complexes (Figure 4-4) was performed.

(27) L = PPh3, X = SnPh3

( 28 ) L = Ph2PCH2CH2NMe2, X = C1

( 29 ) L = Ph2PCH2CH2NMe2, X = SnC13
.Ru (
L\\, ` X (30 ) L = Ph2PCH2CH2NMe2, X = SnPh3
L
( 31 ) L = Ph2PCH2CH2NMe3BF4, X = Cl

(32) L = Ph2PCH2CH2NMe3BF4, X = SnCl3

Figure 4-4. Structure of compounds 27 32.

Synthesis

Synthesis of CpRu(PPh3)2(SnPh3) (27)

The Ru-SnPh3 complex 27 was prepared by reacting CpRu(PPh3)2(SnCl3) (20) in

benzene with an excess of phenyl lithium (Eq 4.1) at room temperature.

CpRu(PPh3)2(SnPh3) was isolated as an air and moisture stable dark yellow solid in 90 %

yield. Replacing the chlorides in CpRu(PPh3)2(SnCl3) with phenyl anions has a profound

effect on the 31P{ 1H} NMR data. The singlet for the equivalent phosphorus atoms is

shifted downfield relative to CpRu(PPh3)2(SnCl3) by approximately 8 ppm to 53 ppm.

The P-Sn coupling is also affected; decreasing by 165 Hz to 270 Hz.


Benzene
+ 4 PhLi Ru.
Ru '//SnPh3
Ph3P- R SnC13 4 hours, RT Ph3P /SnPh3
PPh3 PPh3


20 27 (4.1)









Synthesis of CpRu(Ph2PCH2CH2NMe2)2CI (28)

Attempts at synthesizing complex 28 through ligand displacement from

CpRu(PPh3)2C1 led to product mixtures containing the monosubstituted complex. These

product mixtures were difficult to separate and therefore an alternative route to 28 was

needed. Complex 28 was instead synthesized by reacting Ru(q2-Ph2PCH2CH2NMe2)2C12

with an excess of cyclopentadiene in refluxing ethanol (Eq. 4.2). After 3 days

CpRu(Ph2PCH2CH2NMe2)2C1 was isolated in high yield (74 %) as a yellow solid.

Complex 28 is very stable as a solid or in solution even upon prolonged exposure to air

and moisture. The 31P{ H} NMR spectrum of CpRu(Ph2PCH2CH2NMe2)2C1 is very

similar to that of CpRu(PPh3)2C1, consisting of a singlet at 37 ppm.

Cl
Me2 Me2
N NI
Ethanol Ru
Ru + 3 Cyclopentadiene Ph Pz\\\\'" C1
Lp P 72 hours, Reflux PPh2
Ph2 Ph2

NMe2 NMe2

28 (4.2)

Synthesis of CpRu(Ph2PCH2CH2NMe2)2(SnCl3) (29)

The reaction between CpRu(Ph2PCH2CH2NMe2)2C1 and SnCl2 in DCE (Eq 4.3)

produced CpRu(Ph2PCH2CH2NMe2)2(SnCl3) in near quantitative yield. Complex 29 was

isolated as a yellow solid that was stable to air and moisture not only in the solid state but

also in solution. The 31P{ H} NMR spectrum is very similar to the previously

synthesized Ru-SnC13 complexes, displaying only one singlet at 39 ppm with tin satellite

couplings of 412 Hz.











Ru Ru
.Ru + Cl DCE phzp\h\^' R SnC13
Ph2,P" C1 + 15 SnC12 DCE Ph,P
PPhz2 2 days, RT PPh2


NMe2 NMe2 NMe2 NMe2


28 29(4.3)

Synthesis of CpRu(Ph2PCH2CH2NMe2)2(SnPh3) (30)

Complex 30 was prepared in a similar manner to CpRu(PPh3)2(SnPh3), by reacting

CpRu(Ph2PCH2CH2NMe2)2(SnCl3) with phenyl lithium (Eq 4.4). After workup

CpRu(Ph2PCH2CH2NMe2)2(SnPh3) was isolated in 64 % yield as a yellow solid.

Complex 30 is stable in the presence of air and moisture, not only as a solid but also in

solution. The singlet for the equivalent phosphorus atoms is shifted upfield relative to

CpRu(PPh3)2(SnPh3) by approximately 9 ppm to 44 ppm. The P-Sn coupling

(2Jpsn = 262 Hz) of 30 is unaffected by the change in ligand environment.



Ru Ru
Ph2P\\" SnC13 + 4 PhLi PhP\\ S
PPh | PPh,
PPh2 4 hours, -78 oC PPh


NMe2 NMe2 NMe2 NMe2


29 30 (4.4)

Synthesis of CpRu(amphos)2C1 (31)

CpRu(amphos)2C1 was prepared in a similar manner to CpRu(TPPMS)2C1, by

substitution of triphenylphosphine with amphos. The ligand substitution reaction was

performed in refluxing toluene (Eq. 4.5). After four days of reflux 31 was isolated in 76









% yield as an orange solid. The stability of complex 31 is very similar to that of complex

28, showing no signs of decomposition even after prolonged exposure to air and

moisture. The 31P {H}NMR spectrum of 31 is very similar to that of 28 consisting of a

singlet at 36 ppm.



Ru
Ru, Toluene PPh,
P "P'' Cl + 2.1 Ph2PCH2CH2NMe3BF4 PPh
Ph3P / 96 hours, Reflux
PPh3
NMe3 +NMe3
-BF4 -BF4


19 31 (4.5)

Synthesis of CpRu(amphos)2(SnCl3) (32)

The Ru/Sn complex CpRu(amphos)2(SnCl3) was prepared in an analogous manner

to CpRu(PPh3)2(SnCl3)125 by reacting 31 with a slight excess of SnC12 (Eq. 4.6) in

refluxing ethanol. The resulting yellow solid is stable in air and in solutions exposed to

air and moisture. As expected from the NMR spectrum of

CpRu(Ph2PCH2CH2NMe2)2(SnCl3) (29), the 31P{ H} NMR spectrum of

CpRu(amphos)2(SnCl3) consists of a singlet at 40 ppm with 2Jp-sn = 405 Hz.



Ru Ethanol Ru
Ph 0.. Cl + 1.2 SnC12 Ph2P0" SnCl3
phP 24 hours, Reflux PPh
PPh PPh


+NMe3 NMe3 NMe3 NMe3
-BF4 -BF4 -BF4 -BF4

31 32 (4.6)









As mentioned above, Nafion is a cation exchange polymer capable of acting as a

solid support for positively charged species. Because of this, cationic complexes

analogous to CpRu(TPPMS)2C1 (22) and CpRu(TPPMS)2(SnCl3) (23) were prepared.

The cationic phosphine amphos, was selected as the ligand to replace TPPMS, forming

CpRu(Ph2PCCH2CH2NMe3BF4)2C1 (31) and CpRu(Ph2PCH2CH2NMe3BF4)2(SnCl3) (32).

The neutral complexes CpRu(Ph2PCH2CH2NMe2)2C1 (28) and

CpRu(Ph2PCH2CH2NMe2)2(SnCl3) (29) were also synthesized; these complexes will be

readily protonated by Nafion to form positively charged species.

NMR Data
1H and 31P { H} NMR spectroscopies were utilized to determine the ligand

arrangement about the Ru center. Selected NMR data are presented in Table 4-1. The 1H

Table 4-1. Selected NMR data for complexes 27 32
Cp 31P {H}
Complex Solvent H NMR NMR 2Jp,Sn
(ppm) (ppm) (Hz)
CpRu(PPh3)2(SnPh3) (27) CDC13 4.27 53.0 270
CpRu(Ph2PCH2CH2NMe2)2C1 (28) CDC13 4.29 36.6
CpRu(Ph2PCH2CH2NMe2)2(SnCl3) (29) CDC13 4.71 39.4 412
CpRu(Ph2PCH2CH2NMe2)2(SnPh3) (30) CDC13 4.21 43.8 262
CpRu(amphos)2C1 (31) DMSO-d6 4.48 35.9
CpRu(amphos)2(SnCl3) (32) acetone-d6 5.00 39.5 405
a All NMR data obtained at room temperature.

and 31P{ H} NMR spectral data are very similar to the previously reported complexes

(Table 3-3). Only one singlet is observed in the 31P{ H} NMR spectra for complexes

27 32. The chemical shifts of the cyclopentadienyl protons are a good indication of the

electron density located on the Ru metal center. As observed in the 1H NMR of

compounds 19 23 (Table 3-3), the Cp protons shift downfield as the electron density on

Ru decreases. Hence for CpRuL2C1, the chemical shift of the Cp protons for









L = amphos > Ph2PCH2CH2NMe2 > PPh3 z TPPMS. The same trend was observed for

the complexes containing the SnC13 ligand.

Homogeneous Studies

Cyclic Voltammetry

Cyclic voltammograms of complexes 27 32 each display a single oxidation wave

(Table 4-2). This oxidation process has previously been assigned to the Ru(II/III) couple

for the monometallic [CpRu(PPh3)2Cl,167 (Ind)Ru(PPh3)2Cl,168 CpRu(TPPMS)2C1] and

heterobimetallic [CpRu(PPh3)2(SnC13), CpRu(TPPMS)2(SnCl3)] complexes (Table 3-3).

Based on this assignment, the oxidation waves observed for complexes 27 32 have been

assigned to the one-electron oxidation of Ru(II) to Ru(III).

The amphiphilic nature of the amino-phosphine ligands allow the electrochemical

study of the Ru complexes 28 32 in polar and non-polar solvents. These ligands also

stabilize complexes 28 32 in water. This increased stability was observed during the

characterization of these molecules, and during the CV studies in aqueous solutions

(Table 4-2). This contrasts to CpRu(TPPMS)2C1 (22) and CpRu(TPPMS)2(SnCl3) (23),

both of which are soluble but decompose quickly in water. Due to an inductive effect,

the positive charge on the amphos ligand pulls electrons density away from the Ru metal

center. Because of this the Ru(II/III) oxidation waves of complexes 31 and 32 occur at a

slightly higher potential than 28 and 29, respectively.

The oxidation of the Ru/Cl complex CpRu(amphos)2C1 (31) is chemically

reversible (ipa / ipc Z 1), when analyzed in methylene chloride, methanol, water and

acetonitrile (Table 4-2). The other monometallic complex CpRu(Ph2PCH2CH2NMe2)2C1

(28) is also reversible when oxidized in methylene chloride, methanol and water.








Table 4-2. Formal potentials of complexes 27 32
Complex Electrolyte Epa E12 A ipa / ipc
CpRu(PPh3)2(SnCl3) (20)b 0.7 M TBAT / DCE 1.48 1.44 85 0.92
CpRu(PPh3)2(SnCl3) (20) 0.1 M TBAT/ MeNO2 1.42 1.35 139 1.13
CpRu(PPh3)2(SnCl3) (20) 0.1 M TBAT / CH3CN 1.32, 1.50
CpRu(PPh3)2(SnPh3) (27) 0.7 M TBAT / CH2C2 1.19 1.13 116 1.21
CpRu(PPh3)2(SnPh3) (27) 0.1 M TBAT/ MeOH 1.18
CpRu(Ph2PCH2CH2NMe2)2C1 (28) 0.7 M TBAT / CH2C2 1.13 1.05 134 1.04
CpRu(Ph2PCH2CH2NMe2)2C1 (28) 0.1 M TBAT/ MeOH 0.97 0.90 142 1.13
CpRu(Ph2PCH2CH2NMe2)2C1 (28) 0.1 M KC / H20 0.86 0.80 125 1.07
CpRu(Ph2PCH2CH2NMe2)2C1 (28) 0.1 M TBAT / CH3CN 0.82, 1.14
CpRu(amphos)2C1 (31) 0.7 M TBAT / CH2C2 1.18 1.12 124 1.10
CpRu(amphos)2C1 (31) 0.1 M TBAT/ MeOH 1.00 0.93 114 0.99
CpRu(amphos)2C1 (31) 0.1 M TBAT/ MeNO2 0.92 0.88 90 1.06
CpRu(amphos)2C1 (31) 0.1 M KC / H20 0.85 0.80 108 0.95
CpRu(amphos)2C1 (31) 0.1 M TBAT/ CH3CN 0.86 0.80 113 1.03
CpRu(Ph2PCH2CH2NMe2)2(SnCl3) (29) 0.1 M TBAT / MeNO2 1.65
CpRu(Ph2PCH2CH2NMe2)2(SnCl3) (29) 0.7 M TBAT / CH2C2 1.62
CpRu(Ph2PCH2CH2NMe2)2(SnCl3) (29) 0.1 M TBAT / CH3CN 1.52
CpRu(Ph2PCH2CH2NMe2)2(SnPh3) (30) 0.1 M TBAT / MeOH 1.15
CpRu(amphos)2(SnCl3) (32) 0.1 M TBAT / MeNO2 1.64
CpRu(amphos)2(SnCl3) (32) 0.7 M TBAT / CH2C2 1.70
CpRu(amphos)2(SnCl3) (32) 0.1M TBAT / PC 1.73
CpRu(amphos)2(SnCl3) (32) 0.1 M TBAT / CH3CN 1.59
a All potentials reported vs NHE. Reference 169.