Citation
Synthesis gas transformations with heterogeneous iridium and homogeneous rhodium metal complexes

Material Information

Title:
Synthesis gas transformations with heterogeneous iridium and homogeneous rhodium metal complexes
Creator:
Getty, Cindy S
Publication Date:
Language:
English
Physical Description:
xiv, 179 leaves : ill. ; 28 cm.

Subjects

Subjects / Keywords:
Alkenes ( jstor )
Aluminum ( jstor )
Carbon monoxide ( jstor )
Carboxylates ( jstor )
Catalysts ( jstor )
Chlorides ( jstor )
Infrared spectrum ( jstor )
Iridium ( jstor )
Phosphines ( jstor )
Rhodium ( jstor )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Iridium catalysts ( lcsh )
Rhodium catalysts ( lcsh )
Synthesis gas ( lcsh )
City of Gainesville ( local )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 1988.
Bibliography:
Includes bibliographical references.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Cindy S. Getty.

Record Information

Source Institution:
University of Florida
Holding Location:
University of Florida
Rights Management:
Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Resource Identifier:
024854115 ( ALEPH )
20139539 ( OCLC )
AFM2892 ( NOTIS )
AA00006105_00001 ( sobekcm )

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Full Text













SYNTHESIS GAS TRANSFRWMATIOIS WITH HEIEGENEUS
IRIDIUM AND IHMDGEEUS RHIDIEI METAL OCMPIEXES












BY

CINDY S. GETTY


A DISSERTATION PRESETED TO THE GRADUATE
SCHOOL OF 'ME UNIVERSITY OF FIRI3DA IN
PARTIAL FULFILTMENT OF THE REQUIREMENTS F R
THE DEREE OF DOCITR OF PHIIDSOPHY

UNIVERSITY OF FLRIDA

1988


SOF F LIBRARIES




SYNTHESIS GAS TRANSFORMATIONS WITH HETEROGENEOUS
IRIDIUM AND HOMOGENEOUS RHODIUM METAL COMPLEXES
BY
CINDY S. GETTY
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
1988
¡0 OF £ LIBRARIES




ACKNOWLEDGMENTS
This research and dissertation would not have been possible
without the support, encouragement and guidance of a number of
people. First I would like to thank my mentor, Russell S. Drago and
his wife, Ruth. Had it not been for Doc's "idears" and skill on the
tennis courts, my stay at the University of Florida would not have
been as well-rounded and fulfilling. He always knew I enjoyed a
good argument. Ruth also deserves a special thanks for making me
feel as if Florida was a second heme.
The entire Drago group has also influenced my graduate studies.
A few members have played a special role. I would like to thank Dr.
Keith Weiss, Larry "Chmoo" Chamusco, Jerry "Bear" Grnewald, Thomas
"Them" Cundari, Ngai "Nagy" Wong and my brother Alan "Hard Body"
Goldstein. To Mark "Sparticus" Barnes, I ewe a special thanks for
his friendship which I will always cherish. Dr. Roy King, of the
Microanalytical Laboratories, also deserves a special thanks for all
of his help.
During my undergraduate days at S.U.N.Y. Plattsburgh my studies
in chemistry were greatly influenced by Dr. Gerald F. Kbkoszka.
Without his encouragement I might not be pursuing a career as a
chemist.
iii


Finally, for all of their support and love over the years I
would like to thank my entire family and especially my husband and
best friend, Ed. I always imagined graduate school as a time for
total devotion to one's studies and development as a chemist. Ed
has taught me that there is more to life than chemistry. For this I
am forever indebted to him.
i
iv


TABLE OF CONTENTS
Page
ACKNCWIEDGEMENIS iii
LIST OF TABLES ix
LUST OF FIGURES X
ABSTRACT xiii
CHAPTER
I. INTRODUCTION 1
II. INVESTIGATION OF SUPPORTED IRIDIUM CARBONYL FOR THE
TRANSFORMATION OF SYN GAS AND HC1 TO METHYL
CHLORIDE 3
A. Background 3
B. Experimental 18
Materials 18
Instrumentation 19
Fixed Bed Flew Reactor 20
Preparation of a Phosphinated Support 23
Preparation of the Supported Triphosphine
Substituted Iridium Carbonyl Clusters 24
Preparation of Directly Deposited Tetrairidium
Carbonyl Clusters on the Support 24
Preparation of the Aluminum Chloride Tetrairidium
Carbonyl Cluster Treated Supports 25
Preparation of Other Lewis Acid Deposited
Tetrairidium Carbonyl Clusters 26
Preparation of Aluminum Chloride Treated
Commercial Methanol Catalysts 26
v


Reaction of the Supports and the Supported
Metal Complexes with Carbon Monoxide, Hydrogen
HCl(g) 27
C. Results and Discussion 27
Reinvestigation of Earlier Work of the Supported
Phosphine Substituted Tetrairidium Carbonyl
Cluster 27
Investigation of Directly Deposited Ir4 (00) 12 39
Investigation of Supported lr4(00)12 for Catalytic
Activity Upon Reaction with H2, 00 and HCl(g).... 44
Investigation of the Aluminum Chloride Treated
Deposited Iridium Carbonyl Clusters 47
Investigation of the Aluminum Chloride Treated
Supported Iridium Carbonyl Clusters for Catalytic
Activity Upon Reaction with H2, 00 and HC1 (g) 51
Comparison with the Homogeneous lr4(00)i2-A12C16
System 53
Infrared Investigation of Deposited lr4(C0)12
After Reaction with H2, 00 and HC1 (g) 55
Infrared Investigation of Supported
Ir(CO)io-AloClfi Complexes After Reaction with
H2, 00 and HCl(g) 58
Investigation of Supported IrCl(00)3 Upon Reaction
with H2, 00 and HCl(g) 63
Investigation of Metallic Iridium Upon Reaction
with H2, 00 and HCl(g) 67
Investigation of Other Lewis Acids 68
Investigation of A12C16 Treated Commercial 00
Reduction Catalysts 69
Mechanism Proposed for the Formation of Methyl
Chloride 71
D. Summary 75
vi


III. RHODIUM PERFDJOROCARBOXYIATE TRIHENYLFHOSFHINE
COMPLEXES POR OIEFIN HYl^POEMYIATION 79
A. Background 79
B. Experimental 88
Reagents 88
Instrumentation 89
Synthesis of Tetrakis (acetato) Dirhodium (II) 90
Synthesis of Tetrakis(perfluorobutyrato)
Dirhodium(II) 92
Synthesis of Other Rhodium(II) Carboxylate Dimers. 92
Preparation of Trifluoroacetato
Tris (triphenylphosphine) Rhodium(I) 93
Preparation of Trifluoroacetato
Tris (triphenylphosphine) Rhodium(I) from Hydrido
Tetrakis (triphenylphosphine) Rhodium (I) 93
Preparation of Trifluoroacetato
Bis (triphenylphosphine) Rhodium(I) Carbonyl 94
Preparation of Nafion Supported Rh(02CCF3) (PPh3) 3- 94
Hydroformylation of Olefins with the Rhodium
Ccnplexes 95
C. Results and Discussion 95
Investigation of Rhodium (II) Perfluorocarboxylate
Ccnplexes as Catalysts for Hydroformylation of
1-Hexene 95
Effect of Added Triphenylphosphine on Catalytic
Activity and Selectivity 100
Comparative Studies with Other Rhodium Carboxylate
Ccnplexes 104
Comparative Studies with Rhodium(I) Ccnplexes 107
Investigation of the Rhodium Perfluorocarboxylate
Triphenylphosphine Catalyst System During
Hydroformylation 108
vii


Visible Investigation on the Effect of Added
Olefin and Phosphine to the Rhodium (II)
Perfluorobutyrate Complex 120
Investigation of the Species Formed Upon Reaction
of Rhodium(II) Perfluorocarboxylate Complexes
with Triphenylphosphine 121
Investigation of Rh(02CCF3) (PFh3)3 for Catalytic
Hydroformylation of 1-Hexene 133
Investigation of the Rh(OpCCFo) (Pih-i) -> System
During Reaction 134
Investigation of Trifluoroacetate Carbonyl
Bis (triphenylphosphine) Rhodium(I) 139
Comparative Hydroformylation Studies with Hydrido
Carbonyl Tris (triphenylphosphine) Rhodium(I) 140
Preparation of [Rh(PFh3)3]+[ (020CF3) ] Exchanged
onto Nafion 145
Hydroformylation of 1-Hexene using the Polymer
Supported Rhodium Catalyst 147
Leaching of the Catalyst from the Resin 150
Hydroformylation of Propylene Using
Tris (triphenylphosphine) Rhodium(I) Incorporated
in a Polymeric Membrane Film 150
Hydroformylation of Other Olefins with
Rh(02CCF3) (PEh3)3 151
Hydrogenation of 1-Hexene and Other Miscellaneous
Reactions of CO, H2 and Heptaldehyde with
Rh(02CCF3) (PFh3)3 154
Proposed Mechanism for the Catalytic
Hydroformylation of 1-Hexene with
Rh(02CCF3) (PFh3)3 and Added Triphenylphosphine... 159
D. Summary 162
IV. CONCLUSION 166
REFERENCES 171
BIOGRAPHICAL SKETCH 179
viii


LIST OF TABLES
Table Page
2-1 Ways to Utilize Clusters in Catalysis 5
2-2 Advantages of Homogeneous Versus Heterogeneous
catalysts 8
2-3 Possible Reactions and the Thermodynamic
Feasibility for the Formation of Methyl Chloride. 12
2-4 Major Carbonyl Bands in the Infrared Spectra for
Fhosphine Substituted Ir^OO)^ and Ir4(CO)12.... 29
2-5 Control Reactions for the Fhosphine Substituted
Supported System 31
2-6 Major Carbonyl Bands in the Infrared Spectra for
Fhosphine Substituted Ir4(CO)12 and Ir4(00)i2
After Reaction with H2, GO and HC1 57
3-1 Phosphorus NMR Data for the Rhodium
Ferfluorocarboxylate Complexes 112
3-2 Fluorine NMR Data for the Rhodium
Ferfluorocarboxylate Complexes 115
3-3 Infrared Data for the Rhodium
Ferfluorocarboxylate Complexes 118
3-4 Comparison of 1-Hexene Hydroformylation Activity
for Various Rhodium(I) Catalysts. 135


LIST OF FIGURES
Figure Page
2-1 A Proposed Mechanism For the Formation of Methyl
Chloride with the Phosphine Substituted Supported
Iridium Clusters 17
2-2 A Diagram of the Fixed Bed Flew Reactor 22
2-3 Structure of the Ethoxy Surface Species Formed
During Functionalization of the Alumina Oxide 34
2-4 Schematic Representation of the Decomposition of the
Ethoxy Groups at Elevated Temperatures 37
2-5 Infrared Spectra of lr4(00)12 Deposited onto Alumina
Before and After Treatment with A12C16 41
2-6 Infrared Spectra of Ir4(00) 22 Deposited onto Silica
Gel Before and After Treatment with A12C16 42
2-7 A Sample Gas Chromatograph of the Products Formed
Upon Reaction of H2, 00 and HC1 over the Supported
Iridium Clusters at 125C and 1 Atmosphere 45
2-8 Activity Curves for the Various Supported Iridium
Carbonyl Clusters for the Formation of Methyl
Chloride 46
2-9 Infrared Spectra of lr4(00)^2 Deposited onto Alumina
and Silica Gel After Reaction with H2, 00 and HC1 at
125C 56
2-10 Infrared Spectrum of Al203/Tr4 (00) 12/A12C16 After
Reaction with H2, 00 and HC1 at 125C 60
2-11 Infrared Spectrum of SiO^I^ (00) 12/A12C16 After
Reaction with H2, 00 and HC1 at 125C 61
2-12 ESCA of SiO^I^ (00) 12/A12C16 Before and After Reaction
with H2, 00 and HCl at 125C 62
2-13 Infrared Spectra of Al203/TrCl (00) 3 Before and After
Reaction with H2, 00 and HCl at 125^ 64
x


Fioure
Page
2-14
Infrared Spectra of Al2C>3/IrCl (00) 3/Al2Cl6 Before and
After Reaction with H2, 00 and HCl at 125C
66
2-15
Proposed Mechanism for the Formation of Methyl Chloride
with the Supported Iridium Carbonyl Clusters
72
3-1
A Diagram of the Pressure Bottle Apparatus Used for the
Hydroformylation Reactions
91
3-2
A Sample Gas Chromatograph of the Products Formed After
the Hydroformylation of 1-Hexene with the Rhodium (II)
Perfluorocarboxylate Catalyst at 100C
97
3-3
A Sample Mass Spectra of the Solution After Reaction
Enriched with ^Carbon Monoxide
99
3-4
Activity Curves for the Formation of Heptaldehyde with
Varying Ratios of Rhodium (II) Ferfluorobutyrate to
Triphenylphosphine
101
3-5
Bar Graphs Illustrating the Effect of Added Triphenyl
phosphine on Iscmer Ratio
103
3-6
Comparative Activity Curves for the Hydroformylation of
1-Hexene with Rhodium (II) Ferfluorobutyrate and
Rhodium (II) Trifluoroacetate with Added Phosphine
105
3-7
Color Changes Observed During Reaction
109
3-8
3 ip NMR Spectrum of the Reaction Mixture During
Hydroformylation with Rh2(020C3F7)4 and 5PFh3
111
3-9
19F NMR Spectrum of the Reaction Mixture During
Hydroformylation with Rh2(020C3F7)4 and 5PEh3
114
3-10
Infrared Spectrum of the Reaction Mixture During
Hydroformylation with Rh2 (020C3F7) 4 and 5PFh3
117
3-11
Visible Spectral Overlay Upon Sequential Addition of
1-Hexene to Rhodium (II) Ferfluorobutyrate
121
3-12
Visible Spectral Overlay Upon Sequential Addition of
Triphenylphosphine to Rhodium(II) Ferfluorobutyrate...
123
3-13
Infrared Spectrum of Rh(02CCF3) (PPh3)3
127
3-14
19F NMR Spectrum of Rh(02CCF3) (PPh3)3
129
3-15
31P NMR Spectrum of Rh(02CCF3) (PEh3)3
132
xi


Page
Figure
3-16 Infrared Spectrum of the Reaction Mixture During
Hydroformylation of 1-Hexene with Eh(C>2CCF3) (Pih3)3... 138
3-17 31P NMR Spectrum of the Reaction Mixture During
Hydroformylation of 1-Hexene with Rh(02CCF3) (PPh3)3... 142
3-18 Bar Graph Comparison of the Hydroformylation Activity
of Rh(C>2CCF3) (PFh3)3 Versus RhH(OO) (PEh3)3 143
3-19 Bar Graph Comparison of the Homogeneous Versus the
Heterogeneous Hydroformylation System 149
3-20 A Sample Mass Spectrum of the Reaction Solution After
Hydroformylation of Styrene 153
3-21 A Sample Mass Spectrum of the Reaction Solution After
Hydroformylation of Ethyl Vinyl Ether 156
3-22 Proposed Mechanism for the Hydroformylation of Olefins
with the Tris(tripherylphosphine) Rhodium(I)
Trifluoroaoetate System 160
xii


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 Fhiloscphy.
SYNTHESIS GAS TRANSFORMATIONS WITH HETEROGENEOUS
IRIDIUM AND HCMDGENEOUS RHODIUM METAL CDMP1EXES
By
Cindy S. Getty
December 1988
Chairman: Russell S. Drago
Major Department: Chemistry
There has been a great deal of interest in the development of
chemicals frcrn synthesis gas (H2 and 00). Typically, the reactions
are catalyzed by soluble (homogeneous) metal complexes or supported
(heterogeneous) metal complexes or metal particles. The emphasis of
this work has been on the development of homogeneous and
heterogeneous catalytic systems capable of the indirect
transformation of H2 and 00 into chemicals under mild reaction
conditions.
Supported iridium carbonyl and aluminum chloride were
investigated in an attempt to heterogenize an analogous homogeneous
catalyst. The presence of aluminum chloride was found to lead to
cluster interactions resulting in a system capable of selective
reduction of carbon monoxide under mild reaction conditions. When a
gaseous mixture of H2, CD and HC1 was passed over the supported
cluster at 125C, methyl chloride, methane, carbon dioxide and water
xiii


were observed as major products. Unlike the homogeneous analog only
trace C2 products were detected. Infrared spectroscopy was used to
investigate the preparation of the deposited clusters as well as the
iridium species formed on the support during reaction.
The second study involved the investigation of a rhodium
carboxylate triphenylphosphine complex which was found to be an
active, homogeneous hydroforrnylation catalyst. The system
selectively produced more of the linear aldehyde than the branched.
The product selectivity was found to depend upon the amount of
phosphine present. Spectroscopic studies supported that a
bis (triphenylphosphine) rhodium (I) trifluoroacetate carbonyl species
was the active catalyst. Comparative studies with other rhodium
carboxylate complexes and hydroforrnylation catalysts shewed that the
perfluorocarboxylate complexes exhibited greater activity.
xiv


I. INTRODUCTIO
The investigation of fuel sources other than oil has been of
interest since the 1970s. An attractive alternative is coal. The
combustion of coal results in the formation of a gaseous mixture of
hydrogen and carbon monoxide referred as synthesis gas. Synthesis
gas nay be used as a feedstock for the production of chemicals and
fuels.1
A large number of chemicals may be directly or indirectly
produced from synthesis gas.2 In direct processes, no molecules
other than carbon monoxide and hydrogen are employed as the
reactants. An indirect process would involve the combination of
carton monoxide and hydrogen with a third reactant molecule. The
reactant molecule may be an olefin, alcohol, HC1, etc.
Transition metal complexes are generally employed as catalysts
for the conversion of synthesis gas into chemicals.3'4 Typically,
the catalysts are soluble (homogeneous) metal complexes or supported
(heterogeneous) metal complexes or metal particles. Investigation
of the activity and stability of metal complexes that catalyze the
transformation of synthesis gas under mild reaction conditions is of
interest. Reported here are the results of two studies involving
the investigation of transition metal complexes as catalysts for the
1


2
indirect transformation of synthesis gas into chemicals. The first
study involves the investigation of supported iridium carbonyl
clusters as catalysts for the reaction of H2, 00 and HC1 under mild
reaction temperatures and pressures to selectively produce methyl
chloride. The development of a catalytic system for the formation
of methyl chloride based upon synthesis gas would be industrially
attractive. The iridium complexes were studied in an attempt to
heterogenize a homogeneous iridium system reported to produce minor
amounts of methyl chloride during the hydrogenation of carbon
monoxide.5'6 This study allows for a direct comparison to be made
on a system employing a metal complex of well-defined composition
and nuclearity. The stability of the metal clusters when supported,
as well as under conditions employed during catalysis, was also
probed. Infrared spectroscopy was used to investigate the
preparation of the deposited clusters and the iridium species formed
during reaction with hydrogen, carbon monoxide, and HC1.
The second study involves the investigation of a homogeneous
rhodium carboxylate system as a catalyst for the hydroformylation of
olefins. The ability to vary the carboxylate ligands on the rhodium
complex allows for comparisons to be made of the activities of such
systems during catalysis. The effect of added phosphine on the
distribution of reaction products and the stability of the system
was also studied by a variety of spectroscopic techniques. Finally,
comparative studies with commonly employed hydroformylation
catalysts allow for investigation of the industrial potential of the
rhodium carboxylate system.


II. INVESTIGATION OF SUPPORTED IRIDIUM CARBONYL FOR THE
TRANSFORMATION OF SYN GAS AND HC1 TO METHYL CHLORIDE
A. Background
For over a decade there has been a growing interest in the use
of coal as a potential source of chemical feedstocks and fuels.
Such interest was triggered by rising oil prices in the early 1970s
as well as by a growing concern about the eventual depletion of our
oil resources. Unfortunately, coal cannot be directly converted
into fuels. The combustion of coal in the presence of steam results
in the formation of a gaseous mixture of hydrogen and carbon
monoxide7 as shewn in Equation 2-1. This gaseous mixture
H20(1)
C(coal) > 00(g) + H2(g) Hrxn = +176 KJ/mol (2-1)
is referred to as synthesis gas because synthesis gas and not coal
can be converted into chemical feedstocks and fuels in the presence
of a catalyst. Many articles have focused on the use of synthesis
gas as a raw material for industrial chemicals.2'8-11
One of the best known and oldest processes utilizing synthesis
gas to produce gasoline is the Fischer-Tropsch Process.12 This
process employs a heterogeneous metal catalyst containing Fe, Ru or
3


4
Co metal dispersed on a support such as alumina or silica gel as
shewn in Equation 2-2. Depending upon the catalyst and reaction
conditions the products are hydrocarbons, oxygenates or mixtures
thereof.13 A myriad of products are formed in the Fischer-Tropsch
Fe,Ru,Co Hydrocarbon
n(00 + H2) > and (2-2)
Oxygenated Products
Process. The molecular weight distribution of the products is
characteristic of polymerization reactions. The products follow a
Schulz-Flory distribution function such that the probability of
chain growth is related to the rate of chain propagation and chain
transfer.13
Currently, the only large commercial Fischer-Tropsch facility
for the production of gasoline, gas oil and paraffins from coal is
located in Sasolburg, South Africa, where large deposits of coal
resources exist.14 Typical working conditions are 25 atm. at 220-
240C employing an extruded iron catalyst. The wide product
distribution and the lack of economically mined coal deposits have
deterred the use of the Fischer-Tropsch Process elsewhere in the
world.
Research objectives in the area of synthesis gas conversion
have focused on the development of transition metal catalysts
exhibiting high selectivities for the formation of either oxygenated
products15 or lew molecular weight unsaturated hydrocarbons.16 The
use of metal carbonyl clusters as catalysts or catalyst precursors
has been the subject of many reviews.1720 Because of their well-


5
defined composition and nuclearity these clusters may form the basis
for a new generation of highly selective catalysts or catalyst
precursors in reactions such as hydroformylation, hydrogenation,
isomerization, 00 reduction, etc. In clusters, the metal sites are
also subjected to electronic influences of the surrounding ligands
on the metal framework. Analogies between metal carbonyl clusters
and metal surfaces covered with carbon monoxide have been
suggested.18'21'22
There are many advantages for using clusters rather than
mononuclear complexes as catalysts.23'24 The multinuclear nature of
clusters allows 00 and hydrogen to be bonded in neighboring
positions allowing for interaction between metal atoms. In clusters
there are also a number of metal sites available for the bonding of
carbon monoxide. Metal sites in clusters may also be influenced by
electronic changes around the metal framework resulting from
addition of ligands. Shewn below in Table 2-1 are the ways of
utilizing clusters in catalysis.17
Table 2-1. Ways to Utilize Clusters in Catalysis.
Homogeneous Heterogenized Heterogenized
Intact Intact Clusters Cluster-Derived
Clusters in > Anchored or Deposited > Metal Particles on
Solution on Oxide Supports Oxide Supports
Homogeneous systems employing meted, carbonyl clusters as
catalysts or catalyst precursors exhibit high selectivity for the
formation of oxygenated products such as methanol, ethanol and


6
ethylene glycol and operate under extreme pressure conditions (>1000
atm.). Metal carbonyl clusters such as Ru3(00)12,25 Rh^(CD) 1626 and
CO2(00)827 have been used as catalysts for the homogeneous
hydrogenation of carbon monoxide as shown in Equation 2-3.
Ru, Eh, Co
H2 + 00 > CH3CH + C2H5OH + (CH20H) 2 (2-3)
T= 200-300C
The product selectivity observed in these homogeneous systems is
dependent upon a number of factors15 including the reaction
temperature and pressure, solvent characteristics, presence of
specific ligands and the use of promoters. The major disadvantage
with homogeneous catalysts involves the difficulty of separating the
catalyst from the product.
Heterogeneous systems using metal carbonyl clusters as
catalysts or catalyst precursors tend to produce hydrocarbon
products such as alkanes and alkenes. The use of metal carbonyl
clusters as catalysts is very attractive in view of recent reports
in the literature indicating that metal particle size has a
significant effect on the selectivity for <30 hydrogenation.28'29 It
is believed that small metal particles lead to the formation of low
molecular weight hydrocarbon products such as ethane and ethylene.
Once aggregation of these metal particles occurs the formation of
higher molecular weight products similar to those observed in
typical Fischer-Trcpsch synthesis is observed.30 Understanding the
reactivity of the cluster with the support is essential to


7
controlling metcil particle size and determining the chemical
transformations that occur on the way to forming an active catalyst.
When Ru3(00)12 is supported on alumina no oxygenated products
are detected upon reaction with H2 and CD and the formation of Ru
metal is observed31 as shewn in Equation 2-4. The formation of
oxygenated products was observed when Ru3 (CD) 12 supported onto a
basic support such as magnesia as shewn in Equation 2-5. After
catalysis the presence of an anionic cluster, [RugC(CD)16]2 was
identified. The oxygenated selectivity for ruthenium carbonyl
supported on magnesia was suggested to be a result of the presence
of an intact metal carbonyl cluster on the surface.
Ru3 (CD) 32/Al203
Ho + 00 > + Cp-Cm Hydrocarbons (2-4)
200-350C, 21atm.
Ru3 (00) 12/MgO Oxygenates (CH30H + C2H50H)
Hp + 00 > CH4 + Cp-C-in Hydrocarbons (2-5)
200-350C, 21atm.
There have been two approaches used for the development of
catalytic materials from meted carbonyl clusters. One involves
supporting the metal complex such that an intact cluster framework
with the ligands still bound to it is maintained. This type of
catalyst resembles a homogeneous catalyst. A second method is to
decompose the cluster to a metal particle where the particle size
distribution can be controlled by the cluster decomposition. The
first approach allows a better understanding of the material because
techniques such as infrared spectroscopy are available for studying


8
metal carbonyl carpi exes. Hie stability of these intact cluster
catalysts under reaction conditions is often questioned.
A goal of researchers has been to develop heterogenized
homogeneous catalysts or "hybrid catalysts".32 In the development
of hybrid catalysts the presence of an intact supported metal
ocrplex is desireable. By developing such systems many of the
advantages of both homogeneous and heterogeneous catalysts could be
retained. A listing of the advantages of homogeneous and
heterogeneous catalysts is found in Table 2-2. A hybrid catalyst
should exhibit high selectivity and activity as well as exhibit high
thermal stability and ease of product separation.
Heterogenizing metal carbonyl clusters has been the subject of
many reviews.17'33'34 The main routes used to support metal
clusters include: (1) direct surface bonding or physisorption with
an inorganic oxide support; (2) anchoring of the cluster on
functionalized inorganic oxides and (3) entrapment in zeolites.
Table 2-2. Advantages of Homogeneous Versus Heterogeneous
Catalysts
Homogeneous
versus
Heterogeneous
1.more active due to
availability of metal
1. separation of catalyst
from product
2. reproducible
2.minimizes reactor corrosion
3.electronic and steric
properties can be varied
3. high thermal and mechanical
stability
4.more selective


9
The Inmobilization of metal carbonyl clusters has been achieved
by surface bonding or deposition onto inorganic oxide supports. In
seme cases interaction of the cluster with the oxide support has
been established. Ionic and covalent bonding of the cluster with
the support can be employed. Ionic bonding occurs from nucleophilic
attack of a surface hydroxyl group on a CD ligand of the cluster.
Covalent bonding occurs from oxidative-addition of a surface
hydroxyl group with one of the metal-metal bonds of the cluster.
Fhysisorption of the cluster onto the inorganic oxide has also been
shewn to occur. In these systems intact metal carbonyl clusters
have been shewn to be present. The clusters may undergo interaction
with sites present on the support. Ihe type of bonding of a cluster
onto an oxide support is believed to be dependent upon the nature of
the support and its pretreatment.35
Ihe use of a chemically modified support is an alternative
method of anchoring a cluster onto a support. The recent literature
contains many examples of silica and alumina supports that have been
functionalized with reagents of the general formula
(C2H5O)3Si(CH2)nX where X is a donor group capable of coordinating
to metal complexes.36'37 In general two methods of preparation have
been used to anchor clusters onto oxide supports. The first
involves anchoring the cluster via ligand exchange to a
functionalized support. The other method involves preparing a metal
complex bound to a linking agent followed by coupling to an
inorganic oxide surface. These two methods are depicted below in
Equations 2-6 and 2-7.


10
f-0-Si-CH2CH2X > 1-OS-CH2CH2XyLtl_l (2-6)
(OR) 3-Si-CH2CH2XMmITl_1 > ^-0-Si-CH2CH2XMnItl_1 (2-7)
In 1981, Muetterties and ccworkers5 discovered a novel
homogeneous system that catalyzed the conversion of carbon monoxide
and hydrogen into light hydrocarbons (primarily ethane) under very
mild reaction conditions as shewn in Equation 2-8. The catalyst was
Ir4 (CD) Y2 in a molten Al2Cl6-NaCl medium.
There are some significant results from this homogeneous
reaction. The formation of hydrocarbon products was observed with
no oxygenated products detected. Recall that homogeneous systems
containing meted, carbonyl clusters as catalysts or catalyst
precursors typically produce oxygenated products from reaction of
carbon monoxide with hydrogen. The reduction of carbon monoxide
also occurred under very mild reaction conditions of 1-2 atmospheres
pressure and tenperatures below 200C. The mild reaction conditions
necessary for the reduction of carbon monoxide in the homogeneous
Ir4(00)12/Al2Cl6-NaCl
H2 + 00 > C1-C4 Hydrocarbons (2-8)
180C, 1 atm. (CH3C1)
system was believed to be due to the strong Lewis acid solvent. In
this medium bifunctional activation of carbon monoxide could occur
in such a manner that the oxygen end of a bound carbonyl group could
interact with the Lewis acid as shewn in Equation 2-9. These


11
results were confirmed by Coliman et al. and he preposed that the
active catalyst or catalyst precursor in the homogeneous melt system
is IrCl(OO)3.6 The presence of methyl chloride was reported as a
product in the work indicating the consunption of aluminum
M-CSO>A12C16 (2-9)
chloride during the reaction. The methyl chloride was proposed to
be an intermediate formed during the reaction which was involved in
further homologation and hydrogenation reactions to yield the
observed hydrocarbon products.
Methyl chloride is an important chemical exmmodity.38 It is
used in the production of organosilicon compounds, in the production
of tetramethyl lead and as a solvent in the production of
methyloellulose. As a solvent methyl chloride has come into use in
the last 20 years for the elimination of oils, fats and greases from
surfaces.
The industrial production of methyl chloride is accomplished by
two commercial processes.39 These are the methanol-hydrogen
chloride process and the methane-chlorinaticn process as shown below
in Equations 2-10 and 2-11.
HC1 + CH30H > CH3CI + H20 (2-10)
CH4 + Cl2 > CH3CI + HC1 (2-11)
The production of methyl chloride from methanol is done usually
in the gas phase over activated alumina at 200-300C.
Monochlorination of methane is done in the liquid phase using KC1


12
and CuCl melts. In the formation of methyl chloride,
polychlorinated methanes are also produced. Selectivities of 98-
99% are obtained for the methanol-HCl process.
An attractive alternative method for the direct production of
methyl chloride would be from carbon monoxide, hydrogen and hydrogen
chloride as shewn in Equation 2-12.
catalyst
H2 + 00 + HCl > CH3CI + H20 (2-12)
Vannice reports the production of methyl chloride frem
synthesis gas and HCl at 270C and 5 atmospheres pressure on a
catalyst containing supported Group VIII metals on acidic supports
such as alumina.40 Along with methyl chloride, the formation of
multichlorinated methanes, ethane and propane were also reported.
In Table 2-3 is a listing of the possible reactions as well as the
thermodynamic feasibility for the formation of methyl chloride.41
Table 2-3. Possible Reactions and the Thermodynamic Feasibility
(in keal/mol) for the Formation of Methyl Chloride.
CH3OH + HCl > CH3CI + H20 = -7.82 AG400 = "5.98
CH4 + Cl2 > CH3CI + HCl &G298 = -22.89 AG40o = "25.95
2H2 + 00 + HCl > CH3CI + H20 AC^gs = -13.85 AG400 = "6.51
Prior work conducted in this laboratory led to the discovery of
a supported phosphine substituted tetrairidium carbonyl cluster
which was shewn to exhibit high activity for the formation of methyl


13
chloride in the presence of H2, 00 and HC1.42 The reaction
proceeded under very mild reaction conditions of 25-100C and 1
atmosphere pressure as shewn in Equation 2-13.
fo-Si-(CH2) 2-PEh2)xIr4 () 12-x
2H2 + 00 + HC1 > CH3C1 (2-13)
25-100C, 1 atm.
The coordinated metal carbonyl cluster was prepared by an
initial functionalization of the support. This was accomplished via
a condensation reaction of the surface hydroxyl groups of an
inorganic oxide support such as alumina or silica with the ethoxy
groups of the silane, (OEt) 3SiCH2ai2Pi*12,43 as shewn in Equation 2-14.
-j-QH + (OEt) 3SiCH2CH2PFh2 > (0) x-SiCH2CH2PEhh2 + 3C2H5OH
(2-14)
The number of ^j-O-Si bonds between the support and the silane
linkage is represented as x. The remaining alkoxy groups from the
silane are proposed to be hydrolyzed to yield Si-OH and ethanol.43
The phosphine substituted tetrairidium carbonyl cluster was
assembled from the precursor complex as shewn in Equation 2-15.
ij- (0) x-SiCH2CH2PIh2 + Ir (00) 2C1 (H2N-^-CH3)
Zinc, 00
>
2-methoxyethanol
(0) x-SiCH2CH2PEh2) xlr4 (00) 12_x
(2-15)


14
The synthesis and characterization of these supported clusters by
infrared spectroscopy has been previously reported and shewn to
result in the formation of the mono-phosphine and di-phosphine
substituted clusters.44'45
The catalyst was initially tested in a 3:1 Al2Cl6-NaCl melt
salt under reaction conditions similar to those employed for the
previously reported homogeneous lr4(00) ^-A^Clg/NaCl system.
Results similar to those previously reported6 were obtained such
that methane, ethane and methyl chloride were detected as products.
The supported phosphine substituted iridium catalyst was shown to
leach the iridium cluster from the support during the reaction
producing the homogeneous Ir4 (CD) 12-Al2Clg/NaCl system. To
circumvent the problem of catalyst leaching the supported cluster
was tested in the presence of H2, CO and HC1 and in the absence of
Al2Clg/NaCl. In all cases the same activity and selectivity
resulted as previously observed. The activity of this system was
shewn to be dependent upon a number of factors including the degree
of stirring during catalyst preparation, temperature of the reaction
with synthesis gas and HC1 and metal loading.
A later study was conducted to investigate the above effects
with catalyst activity and the cluster stability during reaction.
It was discovered that the previously reported results for the
formation of methyl chloride were clouded by the presence of
adsorbed 2-methoxyethanol which was introduced onto the surface of
the support during preparation of the phosphine supported cluster.46
A number of attempts were investigated to remove adsorbed 2-


15
methoxyethanol which were unsuccessful. Investigation of
alternative routes to synthesize the supported phosphine substituted
tetrairidium cluster resulted in the formation of materials which
did not exhibit the high level of activity and selectivity for the
formation of methyl chloride as the supported iridium cluster
prepared in the presence of 2-methoxyethanol. In these alternative
systems it was proposed that the formation of methyl chloride
resulted frcm the reduction of carbon monoxide.46 Control
experiments shewed that a contribution to the formation of methyl
chloride was due to impurities in the system introduced during
preparation of the catalyst.
Investigation of the material by infrared spectroscopy after
reaction with H2, 00 and HC1 supported the decomposition of the
catalyst to produce multinuclear complexes and IrCl(C0)3. As the
reaction temperature was increased, it was proposed that the
multinuclear iridium complex was converted to IrCl(CO) 3 or Vaska's
complex on a phosphinated support. It was also proposed that the
stabilized multinuclear complex was active for reduction of carbon
monoxide while IrCl (GO) 3 was inactive. A mechanism was proposed
which accounted for the various routes for the formation of methyl
chloride and other products.46 Figure 2-1 illustrates the proposed
mechanism summarizing the formation of methyl chloride from various
routes. Included in the figure are pathways where by impurities in
the system (such as adsorbed 2-methoxyethanol) may decompose to
methyl chloride as well as a cluster fragmentation pathway believed


A Proposed Mechanism for the Formation
of Methyl Chloride from the Phosphine
Substituted Iridium Clusters,


^-irrh2>mif4ico)y
a 200
4
NCI
3
rrafataution
<
llfta load
M.M Ir)
4acapoa 1 Hon
( *y*tM
laparltlaa
M-tOO'C
1-1. Irl
ra4uca4
carbon
paca*
(riachar Tropach Machanlan)^
C Cl C|, I CS. Cl
S: l ,rJ:
N, NCI
^Carbon Monoxide
Reduction Machanii
(Flyura 2 21)


18
to yield methyl chloride via reduction of carton monoxide upon
reaction with H2, 00 and HC1.
Results of the previous studies of the supported iridium
carbonyl cluster suggest that stabilization of a multinuclear
iridium carbonyl ccnplex onto an oxide support could result in the
formation of an active system for the catalytic reduction of carbon
monoxide in the presence of hydrogen and hydrogen chloride to
produce methyl chloride. The formation of methyl chloride from
synthesis gas and HCl(g) under mild reaction conditions would be
extremely attractive from an industrial standpoint. For these
reasons, as well as to get a better understanding of the interaction
of iridium carbonyl clusters with oxide supports and Lewis acids
continued investigation of this system is warranted.
B. Experimental
Materials
Iridium carbonyl, IrCl(CO) 3, and IrCl3*H20 were purchased from
Strera Chemical Company. Hie Lew Temperature Shift (ITS) methanol
catalyst was supplied by United Catalysts. Aluminum chloride,
anhydrous 99.997%, was purchased from Alfa Products. Iron chloride,
anhydrous, and antimony pentachloride were purchased from Aesar.
Aluminum bromide was purchased from Fischer. All metal complexes
were used as purchased unless otherwise stated. Solvents were dried
by distillation over CaH2 or P205 and stored over 4A molecular
sieves. Hie 2-methoxyethanol (Kodak, scintillation grade) was used


19
without further purification. The support material was Fisher, acid
Brockman Activity I (80-200 mesh) alumina, or Davison grade no. 62
silica gel purchased frcm W.R. Grace and Co. This alumina was
determined to have a specific area of 180 n^/g.47 The silica gel
had a specific area of 340 n^/g, a pore diameter of 14nm, and a pore
volume of 1.1 ax?/g. When used for direct bonding of the cluster,
all powdered oxides were first heated under vacuum at 350C for 15
hours to remove water. When used for functionalization the powdered
oxides were dried at 140C prior to use.
All silanes where purchased frcm Petrarch Systems, Inc., and
vised without further purification.
Hydrogen was purchased frcm Aireo. Carton monoxide (CP grade,
99.5%) and hydrogen chloride (isoelectronic grade, 99.99%) were
purchased frcm Matheson Gas Products. The HC1 feed gas was checked
for chlorocarbons which were not detected. All gases were used
without further purification.
Instrumentation
All air sensitive manipulations were performed in an Aldrich
inert atmosphere glove bag. All syntheses were performed under
either a nitrogen or carbon monoxide atmosphere. Infrared spectra
were obtained as Nujol mulls with a Nicolet model 5DXB spectrometer
using NaCl salt plates. The elemental analyses for iridium were
performed by Galbraith Laboratories, Knoxville, Tennessee. Gas
chromatographic analyses were performed by using a Model 940 FID
Varian chromatograph equipped with a 1/8 in. X 8ft. stainless steel


20
Porapak Q column. The column temperature was maintained at 130C.
Gas chromatographic mass spectrometry were performed by Dr. Roy King
of the Microanalytical laboratory, University of Florida,
Gainesville, Florida. Samples were run by using a AEI MS 30 mass
spectrometer equipped with a KDITQS DS55 data station. The system
was equipped with a FYE Unicam 104 gas chromatograph containing a
1/4 in. X 5ft. Porapak Q column. The system was equipped with a
dual magnesium anode X-ray source and a double pass cylindrical
mirror electron analyzer. Data acquisition was controlled by a
Digital PDP computer. All ESCA data were obtained through the
courtesy of Dr. Tom Gentle, Dew Coming Corporation, Midland,
Michigan. The samples were run in a Ferkin-Elmer Model 551
stainless steel ultra-high vacuum chamber equipped with a dual
magnesium x-ray source and a double pass cylindrical mirror electron
analyzer. Data acquisition was controlled by a Digital PDP
computer.
Fixed Bed Flew Reactor
A glass flow system as shown in Figure 2-2 was used to test the
catalytic activity of the supported iridium complexes for
hydrogenation of carbon monoxide in the presence of HCl (g). This
system is similar to that previously described by Weiss.46 The
gases were allowed to enter the system and mix via a three stage
bubbler with teflon needle valves to control the individual gas flow
rates. The CO and H2 gases were bubbled through mineral oil while
the HCl gas was bubbled through sulfuric acid. The catalyst was


Figure 2-2. A Diagram of the Fixed Bed Flew Reactor.




23
placed in a glass tube with a glass frit to hold it in place and the
gases were allowed to flew over the catalyst. Temperatures were
regulated by using a model 123-8 Lindberg thermostated tube furnace.
Sample ports before and after the catalyst allowed for analysis of
1he gases. The gases were collected by using a pressure-lok 2ml
syringe purchased from Precision Sampling Corp. and analyzed by GC.
The addition of a glass spiral trap to the system allowed for
trapping of the gases in a dry ice/acetone slush.
Preparation of a Phosphinated Support
The phosphinated supports were prepared by a procedure similar
to those previously reported in the literature.33'48 Under a
nitrogen atmosphere 5.0 g of dried support such as alumina or silica
gel was added to a stirred solution of 150ml of toluene or benzene.
The mixture was heated to reflux and 0.45ml (1.25X10-3 moles) of 2-
(diphenylphosphino) ethyltriethoxysilane was added by syringe. This
reaction was allowed to continue for 12-15 hours. The
functionalized support was collected by vacuum filtration followed
by successive washing with the toluene or benzene solvent. The
functional ized supports were dried under vacuum at roan temperature
for 24 hours prior to use. For the phosphinated supports the
loading of accessible phosphine substituents was 1.25 X 103 moles
per gram of support. An analogous synthetic procedure was employed
for functionalization of the supports with 2-
(diphenylphosphino) prcpyltrimethoxysilane. The phosphinated
supports are represented as (S)-FEh2 where S= A1203 and Si02.


24
Preparation of the Supported Triphosphine Substituted Iridium
Carbonyl Clusters
The phosphine substituted iridium carbonyl cluster was prepared
by a procedure similar to that reported by Karel and Norton.49 A
total of 1.3g Ir4 (00) 12 was added to a stirred solution of toluene
or benzene solution containing 5.0g phosphinated support (1.25X10-3
moles of phosphine). The reaction was allowed to proceed at reflux
temperature for 24 hours. The brcwn-yellcw resin was collected by
vacuum filtration and dried voider vacuum at room temperature for 24
hours. The characterization of this material by infrared
spectroscopy has been previously discussed.46 This material is
represented as (S)-(PFh2)xIr4 (00) 12_x where xKL,2 or 3.
Preparation of Directly Deposited Tetra iridium Carbonyl Clusters on
the Support
The method used to support lr4(00) 12 was to adsorb the carbonyl
cluster frcm solution onto an inorganic oxide support such as
alumina or silica gel. A total of 0.5g lr4(C0)12 was added to a
stirred or benzene solution of 5.Og support. The reaction was
allowed to proceed at reflux temperature for 15 hours. The yellow
resin was collected by vacuum filtration and washed with solvent
benzene. The cluster deposited supports were dried under vacuum for
24 hours prior to use. The characterization of these materials by
infrared spectroscopy is discussed in the results section. This
material is represented as S/Ir4(00)12 where S= Al203 and Si02.


25
Preparation of the Aluminum Chloride Tetra iridium Carbonyl Cluster
Treated Supports
A total of 0.33g A12C16 was added to a stirred carbon
tetrachloride solution containing l.Og of tetrairidium carbonyl
cluster on alumina or silica gel which had been deposited on the
support as previously described. The reaction was allowed to
proceed for 12 hours at 50C. The Lewis acid treated materials were
collected by vacuum filtration and washed with carbon tetrachloride
solvent. The materials were dried under vacuum at room temperature
for 24 hours prior to use.
Another procedure was also employed to prepare the supported
aluminum chloride tetrairidium carbonyl complexes. This reaction
was conducted under a nitrogen atmosphere. A total of 0.5g A12C16
was added to a stirred solution of l.Og support in carbon
tetrachloride solvent. The reaction was allowed to proceed for 12
hours at 50C. The aluminum chloride treated support was then
collected by vacuum filtration, washed with carbon tetrachloride
solvent and dried under vacuum for 12 hours. The aluminum chloride
treated supports were then reacted with tetrairidium carbonyl
clusters where a total of O.lg lr4(00)12 was added to a stirred
solution of l.Og aluminum chloride treated support in carbon
tetrachloride solvent. The reaction was allowed to proceed for 12
hours under nitrogen. The solids were collected by vacuum
filtration and dried under vacuum at room temperature for 24 hours
prior to use. The Lewis acid treated deposited materials are
represented as S/Ir4 (00) 12/A12C16. The characterization of these
materials is discussed in the results section.


26
Preparation of Other Lewis Acid Treated Deposited Tetrairidium
Carbonvl Clusters
All other lewis acids such as SbCls, FeCl3 and AlBr3 were
reacted with the deposited tetrairidium carbonyl cluster in an
analogous procedure enployed for the reaction with aluminum
chloride. Appropriate amounts of the Lewis acid were added to a
stirred solution of deposited Ir4 (00) 12- The reactions were allowed
to proceed for 12 hours and the solids were collected by vacuum
filtration then dried under vacuum at room temperature for 24 hours
prior to use.
Preparation of Aluminum Chloride Treated Commercial Methanol
Catalysts
The A12C16 treated commercial methanol catalysts were prepared
by using an analogous procedure enployed for reaction of deposited
iridium carbonyl with aluminum chloride. The catalyst enployed had
the composition CuO/ZnO/Al203 (42:47:10). A total of 2.0g of United
Catalysts Lew Temperature Shift (LIS) Catalyst was added to a
stirred mixture of 0.66g aluminum chloride in 50ml of 0C14. The
reaction was allowed to proceed for "15 hours under nitrogen. The
solid resin was collected by filtration, washed with carbon
tetrachloride solvent and dried under vacuum at room temperature for
24 hours prior to use.


27
Reaction of the Supports and the Supported Metal Complexes with
Carton Monoxide. Hydrogen and HClfq)
A total of l.Og of solid material was placed into the glass
fritted reactor tube. The reactor tube was placed into the fixed
bed flow reactor system previously described in Figure 2-2. A
typical reaction was run at 125C with the individual H2:00:HC1 gas
flews at a ratio of 2:1:0.5 combining to give an overall flew rate
of 2ml/30-60 seconds. The reactant and product gases were monitored
by gas chromatography. Investigation of the active species for
carbon monoxide reduction by infrared spectroscopy is discussed in
the results section.
C. Results and Discussion
Re investigation of Earlier Work of the Supported Fhosphine
Substituted Tetrairidium Carbonyl Cluster
The supported phosphine substituted tetrairidium clusters were
prepared as described by Weiss.46 An inorganic oxide such as
alumina or silica gel was functionalized via a simple condensation
reaction of the alkoxy groups of silane and the hydroxyl groups of
the surface of the support as shown in Equation 2-16. Then the
tetrairidium carbonyl cluster was reacted with the phosphino groups
of the functionalized support as shewn in Equation 2-17. These
materials were characterized by infrared spectroscopy and shown to
contain mostly the tri-phosphine substituted cluster as well as some
mono-phosphine and di-phosphine substituted tetrairidium carbonyl


28
clusters as previously described.46 The majorVco bands for the
supported phosphine substituted iridium clusters are listed in
Table 2-4.
(OEt) 3SiCH2CH2PFh2
>
^-0-SiOi2CH2PFh2
(2-16)
Ir4 (00) 22
¡-o-¡
SCH2CH2Pl2)xIr4 () 12-x
(2-17)
Hie supported phosphine substituted clusters were investigated
for catalytic activity in the presence of 00, H2 and HCl(g) at 75C
in the fixed bed flew reactor previously described in Figure 2-2.
Results similar to those previously reported46 were observed upon
reaction of the phosphine substituted cluster with the reactant
gases as detected by chromatography using a Porapak Q column at
130C. The major product observed in these systems is ethyl
chloride which was previously unreported. Other products observed
by chromatography include methane, methyl chloride, ethane and
acetaldehyde. Water and carbon dioxide were also confirmed by
GC/MS. It was found that if the amount of HCl(g) present in the
system was reduced, the identification of ethanol by gas
chromatography was possible.
As described earlier, when the supported phosphine substituted
tetrairidium carbonyl cluster was prepared in the presence of 2-
methoxyethanol solvent from the reaction of the functionalized
support with the iridium precursor complex IrCl (C30) 2 p-toluidine,
methyl chloride was found to be the major product detected upon
reaction of the supported cluster with the gases.42 An in depth


29
Table 2-4. Major V (oo) Bands in the Infrared Spectra for
Fhosphine Substituted Ir4 (OO) ^ and Ir^CO)^.
Ccsrpound
v |3H,
Ref.
Mixture of
M203-(PEtl2) j, 2lr4 (00) 11( 10a
2083 (w), 2070(w), 2053(s)
2030(S), 2020(S), 2000(s)
1845(w), 1825 (m), 1795 (w)
42,46
Al203-(PEh2)3Ir4(C0)9b
2045(S), 1995(vs), 1791 (m)
1774 (w)
46
Ir4 (00) 22
2073(sh), 2059(s), 2020 (m)
2000 (w)
c
Ir4(C0)12
2075(w), 2058(S), 2020(m)
2003(VW), 1994 (W)
Al203/Ir4(00)12
2075(w), 2062(S), 2022 (m)
1996(W)
Si02/Ir4(CD)12
2075sh), 2063(s), 2023(m)
1996(w)
Al203/Ir4(C0)12/Al2Cl6
2127(W), 2105(mw), 2062(s)
2022(m), 1996(w)
Si02/Ir4(0D)12/Al2Cl6
2111(W), 2075(Sh), 2063(s)
2041(W), 2023(m), 1996 (W)
Al203/IrCl(CO)3
2082(s)
Al203/IrCl (00) 3/Al2Cl6
2071(S)
a= cluster formed by reduction of IrCl(00)2(p toludine)
b= cluster formed by substitution of carbonyl ligands in Ir4(CO)12
c= Crawford, et. al. J. Catal.. (1983), 83, 454.
* s=strong, m=moderate, w=weak, sh=shoulder


30
investigation of that system revealed that the methyl chloride
product resulted from cracking of residual 2-methoxyethanol adsorbed
onto the surface of the oxide support during preparation of
phosphine substituted cluster.46 A series of control reactions were
conducted on the system containing the supported phosphine
substituted iridium cluster50 prepared from reaction of the
phosphino groups of the functionalized support with the carbonyl
groups of the tetrairidium carbonyl cluster as shewn in Equations 2-
16 and 2-17. These experiments were conducted in order to determine
if carbon monoxide was being reduced catalytically.
A series of control reactions were conducted on the system
containing the supported phosphine substituted iridium cluster50
prepared frem reaction of the phosphino groups of the functionalized
support with the carbonyl groups of the tetrairidium carbonyl
cluster as shown in Equations 2-16 and 2-17. These experiments were
conducted in order to determine if carbon monoxide was being reduced
catalytically. The necessity for investigation of all the possible
routes for the formation of methyl chloride is obvious in view of
the activity of the previously described activity reported by
Miller.42 The production of methyl chloride in these systems could
result from adventitious carbon sources introduced into the system
during preparation of the catalyst. The reactions conditions
employed are those expected to lead to reduction of 00 in a
catalytic system.
The results of these experiments are found in Table 2-5.
Contained in Table 2-5 for comparison are the previously described


Table 2-5.
SUPPORT
1 Al -PPhjIrntCO),,
and
A1 (-PPh^jIr^CO)
2 A1 -PPh2
or
SC -PPh2
3 A1203 or
sio2
Control Reactions for the Fhosphine Substituted
Supported System.
MOLES PROD.
SEC"1 CRAM
PREPARATION PRYING PROCEDURE CAS FLOW PRODUCTS CATALYST"1
2-methoxyethanol under AO pal
vacuus
AO
C, 12 hra.
h2/co/hci
CH^CH^Cl
-uf12
CO at 90 C from lr(CO)2 -
CH3C1 at
75
c
-10-10
Cl p-toluldlne
stirred with 2-aethoxyethanol
s
o
c
i
AO
C. 12 hra.
h2/co/hci
CH3C1 at
75
c
-10'10
uider AO pal CO at 90 *C
vacuus
80
C, 12 hra.
h2/co/hci
CH3C1 at
75
c
-1010
2-nethoxvethanol under ACX pal
s
o
c
fi
AO
C, 8 hra.
h2/co/hci
ch3ci
-lO*10
CO at 90 *C
at 60 *C


Table 2-5 Continued
SUPPORT
U A1 -PPh2
5 A1 -PPh2
6 A1 -PPh2
MOLES PROD.
SEC1 cram
PREPARATION
DRYING PROCEDURE GAS FLOW
PRODUCTS
CATALYST"1
reflux in toluene using
victim AO C. 12 hra. H2/C0
CHjOH at 60
C
-10" n
(OCH3)3S-C3H6PPh2
H^CO/HCl
CH3C1 at 60
c
-10"11
reflux in toluene using
(OCH2CH3)3S1-CjH^PPh2
vacuum 80 *C, 12 hrs. H2/C0
CH3CH2OH at
0

0
vO
1
0
1
0
1
0
1
H2/C0/HC1
CH3CH2C1 at 60 C
CHjCH^Cl,
CH3C1 at 100 C
-10"' 10-"
-10"'0 io"n
-10"10 10"
h2/hci
CH^HjCl,
ch3ci
-10"0 io"u
-10"11 10*12
T > 100 *C
reflux in benzene using
vacuus 80 *C, 12 hra. H2/C0
CH3CH2OH at
60 *C
1
0

0
(OCH2CH3)3-SlC2K,PPh2
H2/C0/HC1
CH3CH2C1
at 100 C
1
0
1
0
1
0
1
h2/hci
ch3ch2ci.
1
0
1
0
1
0
1
CH3C1 at
-10"13
T > 150 *C
u>
to
Notes In 1 end 2, A1 -PPh2 was first prepared from reaction or A1203 with (OCH^H^Sl-CgHjjPPhj refluxing benzene.
SC -PPh2 was prepared In a similar manner using S102.
In 1, 0.31% iridium loading.


33
results from cracking of 2 -methoxyethanol solvent over the inorganic
oxide support. The results of the control experiments involving the
cracking of 2-methoxyethanol by HC1 to produce methyl chloride are
shewn in experiments 1-3. As shewn in the Table, ~1010 mol CH3CI/
sec/g material was observed even in absence of the iridium cluster.
As previously described the amount of observed CH3CI in these
systems was dependent upon a number of factors including the degree
of stirring during preparation, loading of the phosphino silane, and
the amount of HC1 present in the reactant gas. The results of these
control experiments indicate that the formation of methyl chloride
is a result of the cracking of 2-methoxyethanol solvent used to
prepare the supported phosphine substituted cluster.
In Table 2-5, experiments 4 and 5 were conducted in an attempt
to investigate the possibility that alkoxy groups from the
functionalizing agent could lead to the formation of alkyl chloride.
Alumina was functionalized with (CH3O) 3SiC3HgP(CgH5) 2 and
(C2H50) 3SiC2H4P(C6H5) 2 in toluene and benzene solvent (experiments
4-6). In both instances the alcohol corresponding to the alkoxy
group was detected when H2 and 00 were passed over the
functionalized support at 60C. The alkyl chloride was observed
when the gas mixture of H^/OO/HCl was passed over the same support.
These observations are interesting in view of the reaction reported
by Waddell et al.43 and by Studer and Schrader.44 In these
articles, the alkoxy groups in (alkoxy) 3Si(CH2)xPPh2 are reported to
be hydrolyzed off of the silicon in the course of functionalization
producing the alcohol and forming hydroxyl groups bound to the


34
V"
HCH
HC
I
Si-
0
H
OvCH2CH3
%
\
''HO
H H
I I
O-C-C-H OH
I I
H H
7/////////////////////7T777
Figure 2-3. Structure of the Ethoxy Surface Species Formed
During Functionalization of the Alumina Oxide


35
inorganic oxide. If this hydrolysis occurs, the alumina surface
retains the alcohol or alkoxy groups as shewn in Figure 2-3. The
alcohol products corresponding to the alkoxy groups from the silane
are obtained upon reaction with H2 and 00 and upon addition of HC1
to the reactant gases the corresponding alkyl halides ene formed
(experiments 4-6).
When a gas mixture of H2/OO/HCI was passed over the support
functionalized with (C2H50)3SiC2H5P(C5H5)2 in toluene (experiment 5)
at 100C, methyl chloride was observed. This product was not
detected when benzene was used instead of toluene as a solvent
during the functionalization procedure. The formation of methyl
chloride in addition to ethyl chloride was detected in the benzene
preparation when H2 and HC1 were passed over the solid at
temperatures greater than 150C. Although at temperatures of 100C
the formation of methyl chloride is detected from the toluene
preparation (experiment 5), the same preparation in benzene
(experiment 6) did not result in the detection of methyl chloride at
this temperature. In the benzene preparation, methyl chloride
production was observed only at temperatures above 150C. It is
possible that the methyl chloride is produced from the cracking of
toluene in experiment 5. The detection of CH3C1 above 150C in
experiment 5 is believed to occur from decomposition of the ethoxy
groups present on the phosphino silane, or on the alumina surface
and cracking of benzene does not appear to occur.
As discussed previously46 the cracking of toluene to produce
methane (and benzene) is thermodynamically possible. This type of


36
reaction could result in the formation of methyl fragments on the
surface of the support which then react with HCl(g) present to
produce methyl chloride. As shown in Table 2-4, the quantity of
methyl chloride formed in the experiments conducted in the absence
of 2-methoxyethanol is lew.
A reaction scheme corresponding to the decomposition of the
ethoxy groups from the phosphinosilane to form CH3C1 is represented
in Figure 2-4. In this scheme, reaction of the adsorbed ethoxy
groups would lead to ethanol production. Dehydration of coordinated
ethanol or ethoxy groups would result in the formation of ethylene
while dehydrogenation of ethanol produces acetaldehyde.
Acetaldehyde is detected in the early phases of the experiments by
GC and GC/MS. Ethylene/ethane is detected throughout the experiment
as a minor byproduct. As shewn in Figure 2-4, ethylene may then
react with HC1 to produce ethyl chloride which is the major product
frem the reaction of ethanol or ethoxy groups with HC1. Ethylene
may be cracked over the alumina surface producing carbon species.
Reaction of the carbon species with hydrogen and HC1 would account
for the methane and methyl chloride observed in the experiments with
the ethoxy silane. All of these reactions are further complicated
by reactions involving the intermediate species. Evidence for such
a scheme is supported by reports in the literature. Several reports
indicate that ethanol can be converted over inorganic oxides to
ethylene,51-53 ethane,51 and acetaldehyde54'55 all of which were
observed as minor products in the reactions. It is generally
recognized that olefins are an important source of carbon formation


37
HO OCHjCH
2^' '3
T>I50C / \ + CH,CH,OH
W7/// 77777
CH.CHO
H, ^
3^ii2v^ii -H20 CH2 = CHz
ch2=ch2-
HCI
CARBON SPECIES
Hg. HCI
Hj
CH*CI
CH3CH2CI
CH<
Figure 2-4. Schematic Representation of the Decomposition
of the Ethoxy Groups at Elevated Temperatures


38
involved in catalytic cracking.56 Reports indicate that over a
metal surface ethylene may decompose to carbon atoms via an
acetylene intermediate.57'58 It is proposed that similar chemistry
is occurring whereby decomposition of ethoxy groups eventually lead
to the formation of methyl chloride.
In order to determine if the methyl chloride or other products
detected are being produced from the catalytic reduction of carbon
monoxide with H2 and HC1 it is necessary to remove the organic
residues from the surface of the supported iridium clusters. An
initial method of investigation in this work involved passing a
gaseous mixture of H2 and HCl over the phosphine functionalized
support at 150C until ethyl chloride or other products were no
longer detected in the exit gas. Reaction of the HCl treated
material with Ir4 (00) 12 in refluxing resulted in supporting the
intact cluster. Upon passing a gaseous mixture of H2, CO and HCl
over the supported cluster at 70C, no products corresponding to
those expected fran the reduction of carbon monoxide or from organic
residues introduced during synthesis were detected.
These results of the reinvestigation of the earlier work42'46
on the phosphine supported iridium cluster indicate that any
reduction of CO by the system is masked by the presence of organic
residues adsorbed onto the surface of the oxide support. These
residues were shewn to be introduced into the system during
preparation of the material. The support functionalization
procedure was shewn to cause the most misleading results in the
previously reported study. It was shown that through a series of


39
control experiments50 (see Table 2-5) that the decomposition of the
alkoxy groups present on the phosphinosilane linking agent led to
the formation of significant amounts of halogenated products.
Attempts to remove these residues by treating the supports with H2
and HCl(g) resulted in the formation of inactive materials for
reduction of carbon monoxide.
Another approach was undertaken to support the iridium cluster.
The objective of this study was to prepare the supported iridium
carbonyl cluster in the absence of any organic residues as well as
to optimize conditions for the bifunctional activation of carbon
monoxide. The main approach was to prepare a heterogeneous analog
to the reported Ir4 (00) j^/A^Cls-NaCl system previously reported by
Muetterties et al.5 and Coliman et al.6 This was originally the
goal of the previously described systems however the difficulties
encountered (which were described above) caused the original
objective to be unattainable.
Investigation of Directly Deposited Ir^(00)12
In order to eliminate adventitious carbon sources in the
system, lr4(00)12 was directly deposited onto an inorganic oxide
support such as alumina or silica gel. First the oxide support was
heated under vacuum at 300C to remove any water or organic residues
which may be present and then the tetrairidium carbonyl cluster was
adsorbed from benzene solution onto the surface of the oxide support
as shewn in Equations 2-18 and 2-19.


40
-h2
AI2O3 > A1203 (2-18)
Al203 + Ir4 (CO) 12 > Al2O3/Ir4(O0)12 (2-19)
The directly deposited iridium cluster was characterized by
infrared spectroscopy. The infrared spectrum of lr4(00) 12 adsorbed
caito alumina is shewn in Figure 2-5A and the major V oo bands ate
listed in Table 2-4. A similar infrared spectrum was obtained for
reaction of Ir4 (00) 12 with silica gel (see Figure 2-6A). The four
band pattern present in Figures 2-5A and 2-6A are indicative of
iridium carbonyl both in the solid state and in solution. It is
proposed that aggregates of Ir4 (00) 12 exist on the support. The
broad absorptions in the 2100-2200 cm-1 region probably involve
molecules on the surface of the aggregate interacting with acid
sites on the support.
Assignments of the metal carbonyl stretching modes for
Ir4 (00) 12 have been reported by Abel and ocworkers.59 As noted
previously,60 the spectrum of lr4(00)12 in the solid state closely
resembles supported Ir4(00)12 although improved resolution in this
and previous work has revealed some differences in the relative
intensities of the bands compared to those previously reported by
Abel.59 The 2062 and 2022 cm-1 bands of Ir4(00)12 in the solid
state and on alumina and silica supports are assigned to the two T2
infrared-active carbonyl stretching modes. Abel attributed the 1995
an-1 band to the T3 mode which is infrared inactive in exact
symmetry, ixlt which becomes active on a slight distortion towards


% TRANSMISSION
41
a = I 996 cm'
b = 2022 cm'
c = 2062 cm"
d = 2075 cm"
e = 2105 cm"
f =2127 cm"
Figure 2-5. Infrared Spectra of Ir4(00)i2 Deposited onto Alumina
(A) Before and (B) After Treatment with A12C16.


Vo TRANSMISSION
42
Figure 2-6. Infrared Spectra of Ir4 (00) ^2 Deposited onto Silica
Gel (A) Before and (B) After Treatment with A12C1&


43
E>2ci symmetry. This band is observed in the solid but not in
solution.59 We observe the 1995 cm-1 band and also observe one at
2075 cm-1 for lr4(00)12 on alumina and silica. The appearance of
the 2075 can-1 band observed in our ccnplexes could be due to further
splitting of the T2 mode (which contains the E mode of the M(00) 3
unit) by distortion toward lower symmetry.
The spectra of iridium carbonyl deposited onto alumina and
silica gel exhibit strong 2062 and 2022 cm-1 absorbances
respectively indicating that most of the material present on the
support is Ir4 (CD) 12.
Investigation of Supported Ir^(00)for Catalytic Activity Upon
Reaction With H2. CP and HCl(g)
The deposited iridium carbonyl clusters were investigated for
catalytic activity for reaction with H2, 00 and HCl(g) using the
fixed bed flew reactor previously described and shewn in Figure 2-2.
Upon passing a gaseous mixture of H2, 00 and HC1 over the supported
Ir4 (00) 12 cluster the formation of methane, ethane, methyl chloride,
acetaldehyde, ethyl chloride and minor amounts of dichloromethane
were detected by using gas chromatography as shewn in Figure 2-7.
GC/MS of the product gas stream also confirmed the formation of
carbon dioxide and water. The major product formed in this system
is methyl chloride. The activity of the Al203/Ir4 (00) 12 system for
the formation of methyl chloride is between 1011 to 1012 mol
CH3Cl/g/sec. A plot of the formation of methyl chloride versus time
is shewn in Figure 2-8. The observed activity of the system is
similar to that previously reported for the phosphine


44
a= methane
Figure 2-7. A Sample Gas Chrcmatograph of the Products Formed
Upon Reaction of H2, GO and HCl(g) over the Supported
Iridium Clusters at 125C and 1 Atmosphere.


45
TIME (HOURS)
Figure 2-8. Activity Curves for the Various Supported
Iridium Carbonyl Clusters for the
Formation of Methyl Chloride.
(A) Al2O3/Ir4(C0)12/Al2Cl6
(B) Si02/Ir4 (00) 12/A12C16 (C) Al2O3/Ir4(C0)12


46
substituted supported iridium carbonyl clusters prepared with the
ethoxy silanes.44 In the previously reported system organic
residues present on the support were shewn to contribute to the
CH3CI formed.
In the directly deposited system the absence of these organic
residues confirms the reduction of carbon monoxide either from the
reactant gas or fren the carbonyl groups directly bound to the
original cluster. While a complete mass balance was not conducted
the total moles of detected product in this system is significantly
less than the number of moles of CD from the original supported
cluster. These results suggest that the observed products are
primarily from deccnposition of the cluster.
Adsorbed metal carbonyl clusters will react with the surface
hydroxyl groups present on inorganic oxide supports.60'61 This type
of interaction has been reported to occur for adsorbed iridium
carbonyl on alumina supports. Iridium carbonyl, Ir4(CO)12, may
undergo a decarbonylation reaction with surface hydroxyl groups at
temperatures above lOO0^0 as shewn in Equation 2-20. The carbon
Ir4(C0)12 + XSOH > Ir4(a0)12_x(S0H)x + xCO (2-20)
monoxide evolved is then preposed to undergo reduction in the
presence of H2 and HC1 to produce the observed products.
The thermal decomposition of supported iridium carbonyl on
inorganic oxides such as alumina or silica has been previously
investigated.62"64 Studies in flowing H2 of lr4(00)12 on Al203


47
resulted in the evolution of 00 and CH4 as well as small amounts of
C2H4, C2Hg and CC^. It was reported that lr4(00)12 does not lose
its 00 groups until 125C. The initial decomposition of the metal
carbonyl cluster was believed to occur through both the interaction
of the cluster with the surface hydroxyl groups of the support as
well as direct hydrogenation of the carbonyl ligands. There have
not been any reports of the stability of metal carbonyl clusters in
the presence of H2, CD and HCl. In order to get a better
understanding of the stability of Ir4(CD) 12 under reaction
conditions an infrared study was conducted. These results are
discussed in a later section.
Investigation of the Aluminum Chloride Treated Deposited Iridium
Carbonyl Clusters
The aluminum chloride treated lr4(00)^2 cluster materials were
prepared by reaction of the oxide deposited cluster with aluminum
chloride as shown in Equation 2-21.
Al203/Ir4 (00) !2 + A12C16 > M20yir4(00)12/Al2Cl6 (2-21)
The hydroxyl groups of a support have been shewn to react with
Al2Clg according to the following scheme as shewn below in Equation
2-22.65 This reaction could minimize decarbonylation of Ir4(C0)12
through reaction with surface hydroxyl groups and reduce the
possibility of the reaction in Equation 2-20 occurring with the
Al2Clg treated solids. Further attempts to minimize the occurrence
of a decarbonylation reaction was provided by a second sample


48
preparation method. In this case, the support materials were first
reacted with A12C16 followed by reaction with Ir4 (00) 12 Ibis
- S-O-H
\
2 0 +
/
- S-O-H
ai2ci6
\
-> 2 0
/
"'s\
CH
+ 2HC1
0-A1C1'
(2-22)
method of preparation should minimize the presence of any remaining
hydroxy groups which were not converted to A1C12 groups and prevent
decarbonylation by reaction of hydroxyl groups on the support
surface with carbonyl groups of Ir4 (00) 12 during the A12C16
treatment used earlier.
The aluminum chloride treatment could (i) increase the
stability of the cluster by minimizing cluster interactions with
surface hydroxyl groups upon conversion of the hydroxyl groups to
aluminum chloro groups; (ii) lead to bifunctional activation of
carbon monoxide by forming a Lewis acid adduct with a bound carbonyl
group of the iridium cluster as shewn belcw. The overall result
Ir-C3D > A1C13
of this treatment should produce a material which exhibits greater
stability and activity for the reduction of carbon monoxide. The
results of reaction of these materials with H2, CO and HC1 are found
in a later section.
These materials were investigated by infrared spectroscopy.
The infrared spectrum of iridium carbonyl deposited onto alumina and


49
silica and then treated with aluminum chloride are shewn in Figures
2-5B and 2-6B respectively. The major V (qo) bands in the infrared
are listed in Table 2-4. The infrared spectrum of the silica
supported cluster is essentially unchanged by reaction with A12C16
except for the appearance of very weak peaks at 2111 and 2041 cm-1.
More pronounced changes occur in the infrared spectrum when
Ir4 (00) i2 supported on A12C>3 reacts with A12C16 as shewn in Figure
2-5B. The spectrum has a high frequency peak of weak intensity at
2127 an-1 and one of moderate intensity at 2105 cm-1. These peaks
have replaced the broad absorption in Figure 2-5A. They are
attributed to the surface molecules of the Ir4(00)12 aggregate
undergoing discrete interaction with bound A1C12 species instead of
a variety of surface acid sites. The infrared spectra of the
aluminum chloride treated supports that were subsequently reacted
with Ir4 (00) i2 did not show any differences in region from the
materials in which the support was first reacted with lr4(00)12
followed by reaction with Al2Cl6. The 2105 cm-1 peak in the A1203
supported material is presumed due to a discrete species formed by
reaction of seme Ir4 (00) 12 surface molecules with A1C12. These high
frequency peaks are not seen for Ir4 (00) ^ in solution or the solid
state. These findings indicate chemical reactivity of at least some
of the iridium carbonyl clusters when treated with Al2Cl6.
Interaction of the A1C12 group shewn in equation 2-22 with
metal carbonyls would lead to shifts in the infrared.66 Possible
acid-base interactions include: (1) interaction of the oxygen of a
carbonyl group with the Lewis acid resulting in a decrease in V co


50
of that group and a smaller increase in V co f t*16 remaining
uncoordinated (terminal) carbonyls of the cluster or (2) direct
interaction between a metal atan and the Lewis acid resulting in an
increase in the V ^ for all carbonyl ligands. The interaction of
the oxygen of a carbonyl group with the lewis acid has been shown to
result in terminal-to-bridging CD shifts as reported by Shriver and
coworkers for Ru3 (CD) 12 interacting with AlBr367 as shewn in
Equation 2-23.
ACID >
§
(2-23)
A third possibility for an increased carbonyl frequency would
involve oxidation of the iridium cluster.
Correa et al.68 has demonstrated that the Lewis acid sites of
alumina can promote 00 insertion. Upon impregnating alumina with
Mn(CD)5(CH3) the presence of an acetyl species with a cyclic
structure as shewn in Equation 2-24 was detected by infrared
spectroscopy.
AI2O3
Mn(00)5(CH3) >
rapid 25C
CH3
a (OC)MnCrr.O
I :l
Al 0 Al
(2-24)
The A1C12 molecules in contact with the surface of an Ir4 (CO) 12
aggregate probably give rise to the 2105 cm-1 peak for
Al203/Ir4(00)12 (see Figure 2-5B) and the 2041 and 2111 cm-1 peaks


51
for Si02/Ir4 (00) Y2 Figure 2-6B). These peaks could be the high
frequency component of an lr4(00) 12 cluster coordinated to A12C16
coordinating to a metal center or a carbonyl group with the low
frequency component being too weak to be detected. Oxidation of an
iridium center in seme of the surface clusters to a higher oxidation
state can also cause the frequency of coordinated (X) to increase.
Psaro et al.69 reported a 30-40 can-1 increase in the
frequencies of the infrared bands for [0s3(00)n]2- ionicly bound to
the surface of MgO. They preposed that the increase in the carbonyl
frequencies was caused by the interaction of the cluster with a
lewis acid center, probably a magnesium ion surface species. A
similar kind of specific bonding was reported for iron carbonyls
interacting with a proton or with carbocations.67 The fact that the
principle bands at 2062 and 2022 can-1 do not shift for
Ir4(00)12/si2, Ir4(00)12/a1203 or H A12c16 treated analogues
suggests that most of the material exists as aggregated clusters on
the surface of the support. A summary of all the infrared
absorbances in the carbonyl region for the iridium complexes is
found in Table 2-4.
Investigation of the Aluminum Chloride Treated Supported Iridium
Carbonyl Clusters for Catalytic Activity Upon Reaction with H2, 00
and HClfa)
The aluminum chloride treated deposited lr4(00)12 dusters were
investigated for catalytic activity upon reaction with H2, 00 and
HCl(g) using the fixed bed flew reactor previously described and
shown in Figure 2-2. These materials are proposed to represent the


52
heterogeneous analog of the previously reported Ir4(00)12-A12C16
homogeneous system.56
Upen reaction of the supported Ir^OOJj^-A^Clg materials with
H2, 00 and HC1 at 125C high selectivity for the formation of
methyl chloride was observed. The formation of methane, trace C2
products and dichlorcmethane was also detected by gas chromatography
similar to that shown for the Al203/Ir4 (00) 12 system in Figure 2-7.
Carbon dioxide and water were also detected by GC/MS. A comparison
of the activity for the different supported iridium materials is
shewn in Figure 2-8.
The Lewis acid treated materials exhibit reactivity of
approximately two orders of magnitude greater than the deposited
clusters which were not treated. In the deposited iridium carbonyl
clusters which were not treated with aluminum chloride the
reactivity of those material is proposed to represent primarily a
stoichiometric decomposition of the cluster to the observed
products. This activity is believed to be initiated by interaction
of the carbonyl groups of the original cluster with the surface
hydroxyl groups of the support as previously described60 and shown
in Equation 2-20. The lewis acid treated solids described here also
exhibit approximately two orders of magnitude greater reactivity
than the previously reported phosphine substituted supported iridium
clusters.46 In those systems it was shewn that organic residues
present on the surface of the oxide support made a contribution to
the observed products.


53
With time the activity of the supported Ir4(00)12 materials
decreases and eventually reduction of carbon monoxide is no longer
observed to occur as indicated by the absence of products detected
by gas chromatography. These resulting inactive materials were
investigated by infrared spectroscopy in an attempt to determine the
nature of the iridium species formed. A discussion of these results
is found in a later section.
Carear ison with the Homogeneous Ir^ (CD) 12~A12C16 Svstem
In the previously reported homogeneous Ir4 (00) 22-Al2Cl6 system
the major product observed upon reaction with H2 and 00 was
ethane.5'6 No oxygenated products were detected in the homogeneous
iridium system unlike typical homogeneous 00 hydrogenation systems
employing metal carbonyl clusters as catalysts. Other products
detected in that system include methane, methyl chloride and
propane. Coliman et al.6 preposed that the methyl chloride produced
was an intermediate species in the molten system which undergoes
further homologation and hydrogenation reactions leading to the
formation of higher hydrocarbon products. However, in the supported
iridium carbonyl system investigated in this study methyl chloride
was observed to be the major product in the reaction of the
supported iridium clusters with H2, 00 and HCl. This increase in
product selectivity may result from two factors. One would involve
the HCl present in the reactant gases which would convert C]^
intermediates to methyl chloride. The short contact time between


54
CH3C1 and Al2Clg would also minimize subsequent reaction of CH3C1
leading to homologation.6
The catalytic synthesis of hydrocarbons from H2 and CD over
supported iridium metal on alumina has been previously investigated
and shown to produce methane as the major product as well as minor
amounts of ethane, ethylene and methyl chloride.40 The formation of
methyl chloride in the Ir/Al203 system was found to be due to the
presence of chloride ions on the alumina surface after impregnation
of the metal halide.70
Lamb and Gates71 have reported that magnesia supported
H20s(00)4 is active for the catalytic hydrogenation of carbon
monoxide to yield to C4 alkanes. The rate of formation of
methane was reported to be 4.2 x 104 mol hydrocarbon/mol Os/s at
275C and 10 atm. The rate of formation of the C2-C4 products was
reported to be 5 x 10-5 to 7 x 107 mol hydrocarbon/mol Os/s. The
supported iridium carbonyl systems reported here are less active
(8xl0-5 to 9xl0-6 mol methyl chloride/mol lr4(00) 12) but more
selective.
In this iridium system it is proposed that the methyl chloride
is being formed by the catalytic reduction of carbon monoxide or
from a stoichiometric decomposition reaction involving the original
cluster. Under the conditions, the curve in Figure 2-8 would have
to be investigated for over 1000 hours at the activity level seen at
forty hours in order to exhaust all of the 00 originally present in
the cluster. Even from the data reported for similar systems71'5 it
is difficult to differentiate between the occurrence of catalytic 00


55
reduction and cluster decomposition. Experiments with labelled 00
have been shown not to be definitive46 for exchange of 00 with the
clusters and intermediates formed in their decomposition could occur
and lead to labelled carbon products. A discussion of the proposed
mechanism for reduction of 00 in the supported iridium systems
reported here is found in a latter section.
Infrared Investigation of Deposited Ir^ (00) After Reaction with
H2. 00 and HClkh
Infrared spectroscopy was used to investigate the alumina and
silica supported tetrairidium carbonyl clusters after reaction with
H2, CD and HC1 at 125C. The infrared spectrum of Al203/Ir4 (00) 12
and Si02/Ir4 (00) 12 after exposure to the reactant gases is shown in
Figure 2-9 and the major V qq bands are listed in Table 2-6. A
comparison with the original spectrum shewn in Figure 2-5 indicates
that significant changes in the carbonyl region have occurred. The
decrease in intensity of the 2062 and 2022 cm-1 peaks of lr4(00)12
attributable to the tetrairidium carbonyl cluster indicates that
most of the Ir4 (CD) 12 cluster has decomposed. As can be seen in
Figure 2-9 two strong absorbances at 2140 and 2080 cm-1 appear.
This spectrum is attributed to decomposition of Ir4(C0)12 to lower
rruclearity iridium chlorocarbonyl species.
Decomposition of Al203/Ir4 (CD) 12 is believed to be initiated by
reaction at catalytic conditions of the support surface hydroxyl
groups with the carbonyl groups of Ir4 (CD) 12 as reported by Tanaka
et al.60 and shown in Equation 2-20. In their infrared study of the
decomposition of Ir4(CD)^2 on Al2C>3 no absorbences at wavenumbers


% TRANSMISSION
56
Figure 2-9. Infrared Spectra of Deposited Ir4 (00) ^
on (A) Silica Gel and (B) Alumina After
Reaction with H2, CO and HCl(g) at 125C.


57
Table 2-6. Major V (go) Bands in the Infrared Spectra
for Ehosphine Substituted lr4(00)12 and lr4(00)12
After Reaction with H2, 00 and HC1.
Compound
V co* .
(cm-1) Ref.
AI2O3- (PHi2 ) 1,2,3Ir4 () 11,10,9
after reaction at
a) 75C
2150(m), 2102(sh), 2069(S)
2026 (w), 1734(w), 1719 (W)
46
b) 125C
2137(m), 2069(s), 2026(W)
1990(m), 1734 (W), 1719 (w)
46
c) 200^0
2055(s)
46
Al203/Ir4(00)12 after
reaction at 125C
2140(S), 2118 (W), 2082(S)
2022(vw), 1997 (W)
Al2C>3/Ir4 (00) 12/A12C16
after reaction at 125C
2140(m), 2118(m), 2075(sh)
2062(s), 2022(m), 1997(m)
A1203/IzC1 (00) 3 after
reaction at 125C
2118(m), 2075(w), 2062(s)
2022(111), 1997 (w)
Al203/IrCl (00) 3/Al2Cl6
after reaction at 125C
2113(m), 2080(w), 2060 (m)
Ir4(00)12/Al2Cl6-NaCl
2190(S), 2160(S), 2125(S)
2112(m), 1630 (m)
* s=strong, monederate, w^weak, sh=shoulder


58
greater than 2080 can-1 were observed, even after reduction of the
cluster to metallic iridium and subsequent exposure to carbon
monoxide. The appearance of absorptions at wavenumbers greater than
2080 can1 in our results (Figure 2-9) suggests the formation of
discrete chloro carbonyl iridium complexes.
Infrared Investigation of Supported Ir^(CP)-¡o-AloClg Complexes After
Reaction with H2. 00 and HClfq)
As previously discussed and shown in Figure 2-9 supported
Ir4(00)12 on alumina or silica gel supports decomposes to produce
lower nuclearity iridium dhlorocarbonyl species exhibiting an
infrared spectrum which is different from the starting material.
This decomposition was proposed to be initiated by interaction of
the carbonyl groups of the cluster with the surface hydroxyl groups.
The possibility of cluster decomposition by interaction with
hydroxyl groups was investigated by reacting the support material
with aluminum chloride. In this case, interactions between the
surface hydroxyl groups and the carbonyl groups of the cluster
should have been greatly reduced as shewn in Equation 2-22. If the
major decomposition mechanism of the supported clusters involves the
displacement of carbonyl ligands by surface hydroxyl groups, the
conversion of these hydroxyl to aluminum chloride groups65 should
not only increase the acidity of the support material, but should
also lead to an increased stability of the supported Ir4(C0)12.
The infrared spectrum of alumina supported Ir4 (CO) 12 treated
with A12C16 after exposure to H2, 00 and HCl at 125C is shewn in
Figure 2-10 (see Table 2-6 for a listing of the major V ^ bands).


59
The infrared spectrum of silica supported Ir4 (00) 12/A12C16 i-s found
in Figure 2-11. The 2062 can-1 and 2022 cm-1 peaks indicate that
seme of the original Ir4 (00) 12 cluster is still present. The high
frequency peaks and complexity of the spectrum indicate that the
clusters have undergone transformations to produce stabilized
multinuclear iridium chlorocarbonyl species. The possibility of
minor amounts of small metal particles undetectable by infrared
spectroscopy cannot be ruled out.
In the homogeneous Ir4(00)12-A12C16 previously reported,5
infrared spectroscopy was used to investigate the material after
reaction with H2 and 00. A multiband spectrum in the 2100 cm-1
region (see Table 2-6) was found as well as a peak at 1630 cm-1. It
was previously proposed that the lew frequency peak was
characteristic for M^-00-Lewis acid bonding. In the heterogeneous
Ir4 (00) 12/A12C16 system studies here, no bands in the 1900-1600 cm-1
region were observed. It is possible that absorbances corresponding
to bridging carbonyl groups are present but are either too weak or
maskpd by absorbances from the support. Alumina does exhibit a
strong absorbance at 1630 cm-1.
Final evidence suggesting the existence of several iridium
chlorocarbonyl complexes was provided by photoelectron spectroscopy
(ESCA). The materials were investigated before and after reaction
with the gases. The results are shewn in Figure 2-12. At best the
results are qualitative. The data obtained from samples of the
supported clusters after exposure to the reactant gases at 125C
suggested the presence of at least two different oxidation states in


% TRANSMISSION
60
Figure 2-10. Infrared Spectrum of Al203/Ir4 (00) 12/A12C16
After Reaction with H2, 00 and HCl(g) at 125 C.


% TRANSMISSION
61
Figure 2-11. Infrared Spectrum of Si02/Ir4 (00) 12/A12C16
After Reaction with H2, 00 and HCl(g) at 125C.


62
Figure 2-12. ESCA of SiO^I^ (00) 12/A12C16
(A) Before and (B) After Reaction
with H2, 00 and HCl(g) at 125C.


63
the resulting iridium complexes as indicated by a minor shift to
higher binding energy.
Investigation of Supported IrCl(00)3 Upon Reaction with H2. 00 and
HC1M
Coliman et al.6 reported that the mononuclear complex,
IrCl(00)3, was either the active catalyst or catalytic precursor
for 00 conversion in the homogeneous Ir4(00)i2/Al2Cl6-NaCl melt
system. In order to gain further insight into what transformations
occurred in the supported iridium systems and the nature of the
inactive iridium species which may have been formed during reaction
with H2, 00 and HC1, an investigation of supported IrCl(OO)3 was
undertaken. IrCl(00)3 was deposited onto A^O^j (see Figure 2-13A).
Upon exposure of A^O^IrCl (00) 3 to H2, 00 and HOI at 125C only
minor amounts of methyl chloride were formed. The infrared spectrum
of deposited lrCl(00)3 after exposure to H2, 00 and HC1 at 125C is
shewn in Figure 13B and the major bands are listed in Table 2-6.
The four band pattern present in supported Ir4 (00) 12 (see Figures 2-
5 and 2-6) and Al203/Ir4(00)12/Al2Cl6 after exposure to H2, 00 and
HC1 (Figure 2-10) is also present in Al203/IrCl(00)3 after exposure
to the gases.
Fhysisorbed Kh^OO) is easily formed on the surface of a
support by reaction of Rh(I) surface species with 00 in the presence
of a partial pressure of water.72 Chini and Martinengo73 also
O
reported that Eh^OO) was easily synthesized by reaction of
[Rh(00) 2C1]2 with 00 in the presence of water under slightly basic


64
WAVENUMBERS (CM*1)
Figure 2-13. Infrared Spectrum of A^OyTrCl (CD) 3
(A) Before and (B) After Reaction
with H2, CO and HCl(g) at 125C.


65
conditions. Recently, ruthenium and osmium carbonyl clusters have
been prepared by the conversion of supported mononuclear halide
complexes (RuCl3 and H20sCl6 respectively) under conditions of
catalytic hydrogenation of carbon monoxide.74 It is believed that
similar chemistry could occur with the supported IrCl(OO) 3 system.
The mononuclear complex could interact with surface hydroxyl groups
of the alumina support under the conditions of 00 hydrogenation
employed resulting in the formation of a higher nuclearity iridium
carbonyl complex. This type of reaction could result in the
formation of an iridium carbonyl cluster exhibiting an infrared
spectrum similar to Ir4 (00) 12 (see Figures 2-5 and 2-6).
Deposited IrCl(OO) 3 was also reacted with A12C16 (see Figure 2-
14A) and investigated as a catalyst or catalyst precursor. The
2071 cm-1 peak has replaced the broad absorption in Figure 2-13A
and is attributed to surface molecules of IrCl(OO) 3 undergoing a
discrete interaction with bound A1C12 species instead of a variety
of surface acid sites. Upon exposure of Al203/IrCl (00) 3/Al2Cl6 to
H2, 00 and HC1 at 125C only minor amounts of methyl chloride were
formed similar to A^OyTrCl (CO) 3. The infrared spectrum of
Al203/IrCl(00)3/Al2Cl6 after exposure to H2, 00 and HC1 (shown in
Figure 14B) and the major V qq bands listed in Table 2-6) contains
high frequency absorptions at 2113 and 2060 cam1 similar to
Al203/IrCl (00) 3 after exposure to the gases (see Figure 2-13B) but
does not contain any substantial absorptions below 2060 cm-1. They
could be present but are obscured by broad absorptions. The
differences in reactivity for 00 reduction of the supported


% TRANSMISSION
66
A
Figure 2-14. Infrared Spectrum of A^C^j/IrCl (CD) 3/Al2Cl6
(A) Before and (B) After Reaction
with H2, CO and HCl(g) at 125C.


67
mononuclear iridium chloro carbonyl complexes compared to their
homogeneous analog suggest that their chemical reactivities have
been greatly altered upon heterogenizing them.
Investigation of Metallic Iridium Upon Reaction with H2. 00 and
HCl(q)
Either Ir4 (CD) 12 or IrCl3 3H20 was physically adsorbed onto
alumina. Each sample was pretreated by calcination at 250q under
hydrogen for five hours. The resulting gray supports were
investigated for catalytic activity upon reaction with H2, 00 and
HC1 and were observed to produce only a trace amount of methyl
chloride at 125C under H2, 00 and HC1 in a stagnant reactor. An
increase in activity to approximately 2.5 x 10-7 mol CH3CI/ mol Ir/
s was observed for these metallic iridium systems upon raising the
reaction temperature to 200C. The catalytic formation of
halogenated hydrocarbons from synthesis gas and HCl(g) over
inorganic oxide supported iridium metal between 200 1000C has
previously been reported.40
The infrared spectra observed for the metallic iridium systems
exposed to H2, CD and HC1 was observed to contain one broad weak
absorption whose location was dependent upon the extent of metal
loading. The spectra resembled the spectrum of the decomposed
phosphine supported cluster resulting from exposure to the reactant
gases at 200C as previously reported.46 The predominant infrared
absorptions assigned for carbon monoxide absorption onto an iridium
metal surface has been reported to range from 2010 cm-1 at low metal
coverage to 2093 cm-1 at metal saturation.75-77
It was previously


68
concluded frcm the similarities in the infrared spectra of metallic
iridium and the decomposed phosphine supported clusters that
metallic iridium is formed above 200C under a H2, CD and HCl
atmosphere (see Table 2-6). However, below 200C the stabilization
of discrete iridium complexes is indicated by the complexity of the
infrared spectra.46 The results of this infrared study conducted
with the supported Ir4 (00) 12-A12C16 materials after reaction with
H2, CD and HCl suggest that discrete iridium complexes have also
been stabilized on the support. A variety of iridium dhlorocarbonyl
complexes have been reported to be formed by the reaction of
powdered iridium metal with 00 and Cl" ions.78 The possible role of
these stabilized iridium complexes in the reduction of carbon
monoxide is discussed in the mechanism for 00 reduction found in a
later section.
Investigation of Other Lewis Acids
Other Lewis acids were investigated for the preparation of an
Ir4(00)12-Lewis acid solid material capable of catalytically
hydrogenating carbon monoxide with HCl to methyl chloride. The
acids investigated were FeCl3, A1BT3 and SbCls- The activity
observed when the other Lewis acids were investigated was less than
that observed for the aluminum chloride treated material. For the
material treated with iron chloride the conversin of the iron
chloride to iron carbonyl is believed to occur in the presence of
the carbon monoxide reactant gas. This is followed by loss of the
iron carbonyl from the system as indicated from a noticeable yellow


69
coloration of a post bubbler in the flew system. This type of
reaction is not unreasonable considering the volatility of iron
pentacarbonyl. In the case of the aluminum bromide treated iridium
clusters the conversion of the bromide complex to the chloride
complex is believed to occur in the presence of HC1. Even in
these systems the activity for the formation of methyl chloride was
less than the analogous solids prepared form aluminum chloride. The
antimony pentachloride treated materials exhibited the highest
activity for the formation of methyl chloride of the three
alternative acids employed. During the course of the reaction with
H2, 00 and HC1 the formation of metal was observed to occur. This
was evident from plating out of a black mirrored ring above the
solid material in the reactor tube. Attempts to increase the
activity and stability of these systems (by varying the reaction
temperature and amount of added HC1) for the reduction of carbon
monoxide were unsuccessful.
Investigation of A^Clg Treated Commercial 00 Reduction Catalysts
A copper methanol catalyst was investigated for catalytic
activity in the reduction of carbon monoxide with hydrogen and
hydrogen chloride to produce methyl chloride. The Lew Temperature
Shift catalyst (United Catalyst) did not exhibit any activity for
the reduction of carbon monoxide under the reaction conditions
employed even at temperatures of 200C. These result are not
surprising because the materials are reported to exhibit activity at
220-210C and 50-100 atmosphere pressure.79


70
Upon treatment with aluminum chloride these materials did
exhibit activity for the formation of methyl chloride. The activity
of these catalysts was '1010 mol O^Cl/s/g catalyst which is
similar to that observed for the previously described supported
Ir4 (CO) i2Al2cl6 systems. The observed activity for the reduction
of carbon monoxide under mild conditions with the methanol catalysts
is attributed to the bifunctional activation of carbon monoxide
occurring upon treatment with aluminum chloride.
The lifetime of the treated methanol catalysts was observed to
be approximately 8-15 hours depending upon the amount of HC1
reactant gas and the flow rates. A color change in these materials
from brown-black to dark green is accompanied by a decrease in
activity. It is suspected that the decrease in activity is a result
of the formation of copper chloride. These methanol catalyst have
been reported to be sensitive to poisoning by HC1 leading to the
formation of copper chloride79 as shewn in Equation 2-25.
CU-O-Zn + HC1 > CuCl + HOZn (2-25)
Accompanying this change is the accumulation of water in the reactor
tube which leads to the conversion of aluminum chloride to aluminum
hydroxide decreasing any lewis acid interactions. Several
experiments were conducted to try to increase the stability and
activity of these systems for the formation of methyl chloride
including varying the amount of HC1 present as a reactant and
temperature. In all cases the activity of the system would decrease


71
accompanying a color change in the catalysts. It is proposed that
the activity displayed by these systems is due to the Lewis acid
treatment leading to mild reduction of carbon monoxide via a
bifunctional activation mechanism.
Mechanism Proposed for the Formation of Methvl Chloride
A schematic representation summarizing the reaction of H2, CO
and HC1 with all the various supported iridium carbonyl complexes is
shown in Figure 2-15. A series of control reactions completed in
this work support the formation of methyl chloride from organic
residues introduced onto the supported phosphine substituted iridium
complexes during preparation. An infrared study previously
conducted by Weiss46 of these materials before and after reaction
established that decomposition of the phosphine substituted clusters
to lower nuclearity iridium species occurred during the formation of
methyl chloride.
In this work, tetrairidium carbonyl clusters were deposited
onto inorganic oxide supports. These materials were then treated
with aluminum chloride and shown to undergo interactions with Lewis
acid sites present on the surface of the support. Evidence for
these interactions was provided by the presence of new absorbances
in the carbonyl region as indicated by infrared spectroscopy. The
deposited Ir4 (CD) 12 clusters were found to react with H2, CD and HCl
to produce methyl chloride as the major product detected in the post
gas stream. The formation of methane, trace C2 products, water and
carbon dioxide was also detected. The aluminum chloride treated


72
lr,Cly (C0)z
Hz/CO/HCI
200C
METALLIC IRIDIUM
(I r )n CO
Figure 2-15. Propcxsed Mechanism for the Formation
of Methyl Chloride with the Supported
Iridium Carbonyl Clusters.


73
materials were found to be approximately two orders of magnitude
more active for the formation of methyl chloride than the analogous
materials which were not treated with the Lewis acid.
Studies of the deposited iridium clusters after exposure to the
reactant gases indicate that decomposition of the iridium clusters
has occurred during the course of reaction. Infrared spectroscopy
supports the decomposition of the clusters to lower nuclearity
iridium chloro carbonyl species and not to metallic iridium. These
resulting iridium species which are formed during reaction are
eventually inactive for the reduction of carbon monoxide. At
elevated temperatures (>200C) further decomposition to metallic
iridium is observed. The supported metallic iridium materials
exhibit minor activity upon reaction with H2, 00 and HC1 for the
formation of (^-03 hydrocarbons and methyl chloride. The formation
of methyl chloride at temperatures above 200C can be explained by a
Fischer-Trcpsch mechanism as previously described by Vannice.40
It is proposed that the formation of methyl chloride at
temperatures below 200C may result iron a pathway involving the
reduction of carbon monoxide. For the deposited Ir4(C0)12 materials
in the absence of the aluminum chloride treatment it is proposed
that the formation of methyl chloride results from decomposition of
carbonyl groups present on the original cluster. This reduction is
proposed to be initiated via a decarbonylation mechanism from
interaction of the carbonyl groups of the cluster with the hydroxyl
groups of the support (as shown in Equation 2-26)


74
Ir4 (00) 12 + xSOH > Ir4(CX))12_x(SOH)x + xOO (2-26)
followed by subsequent reduction of carbon monoxide to the observed
products. The resulting materials exhibit strong absorbances at
2082 and 2140 an-1 indicative of mononuclear complexes. The
investigation of supported mononuclear IrCl(00)3 for activity for
reduction of carbon monoxide in this work resulted in the formation
of only trace amounts of methyl chloride.
The formation of methyl chloride in the aluminum chloride
treated materials is proposed to be initiated by a bifunctional
activation of carbon monoxide via interaction of the oxygen end of a
bound iridium carbonyl species with aluminum chloride. Subsequent
reaction with H2 and HC1 would lead to the formation of the observed
products. The resulting material after reaction supports the
presence of iridium species which are not mononuclear as indicated
by the complexity of the infrared data. It cannot be ruled out that
decomposition of the supported Ir4 (00) 12-A12C16 materials is not
initiated by interaction of the carbonyl groups of the iridium with
the aluminum chloro present on the surface of the support. It is
proposed that the increased activity for the formation of methyl
chloride for the Lewis acid treated materials is due to the
stabilization of multinuclear iridium species. The stabilization of
multinuclear iridium species in the supported phosphine substituted
iridium complexes were believed to be active for the formation of
methyl chloride in that system.


75
The activity of the deposited iridium carbonyl clusters were
shown to be greater for the formation of methyl chloride than any of
the previously investigated supported iridium systems. Even with
the systems described in this study high levels of activity were not
achieved such that commercial production of methyl chloride based
upen synthesis gas would be attractive.
D. Summary
The investigation of supported phosphine substituted iridium
carbonyl clusters resulted in the identification of organic residues
on the surface of the inorganic oxide support which were
incorporated during preparation. The presence of these residues was
shown to result in the formation of alkyl halides (CH3CH2CI and
CH3CI) upon reaction with H2, CO and HCl. The results of control
experiments suggest that the previously reported activity for the
formation of methyl chloride from reduction of CO with H2 and HCl by
these systems were clouded by the presence of carbon sources
introduced during the support functionalization procedure.50
A study was undertaken whereby Ir4(CO)12 was deposited on to
inorganic oxide supports such as alumina and silica gel and also
treated with aluminum chloride. The characterization of these
supported clusters was conducted by infrared spectroscopy. The data
obtained suggest that Ir4(CO)12 remains intact upon deposition onto
the oxide supports and exhibit spectral features common to Ir4(CO)12


76
in the solid state and in solution. Upon reaction of the deposited
iridium clusters with aluminum chloride the appearance of high
frequency bands in the infrared spectra of these materials was
observed. These data suggest that the supported iridium carbonyl
clusters have undergone interactions with strong Lewis acid sites
present on the surface of the support.
The supported iridium carbonyl clusters were investigated for
catalytic activity for reaction with H2, CD and HC1 to produce
methyl chloride. Precedence for this reaction is provided from a
report of a homogeneous CD hydrogenation system where methyl
chloride was produced though ethane was the major product reported.
The reported catalyst was Ir4(CD) 12 in a molten Al2Cl6-NaCl
medium.56 The mild reaction conditions (1-2 atmosphere pressure
and temperatures below 200C) necessary for the reduction of carbon
monoxide in the homogeneous system were believed to be due to the
strong Lewis acid solvent where bi functioned, activation of carbon
monoxide could occur. The supported iridium carbonyl clusters
treated with aluminum chloride are this researcher's version of the
homogeneous Ir4(CD)12-A12C16 system. These materials were
investigated for the reduction of carbon monoxide with H2 and HC1 at
1 atmosphere pressure and 125C. The supported iridium carbonyl
clusters were found to result in the formation of methyl chloride as
the major product which was quantified, unlike the homogeneous
system where, ethane was the major product reported. The formation
of methane, ethane/ethylene, acetaldehyde, ethyl chloride, methylene
chloride, carbon dioxide, and water were also detected in the


77
supported Ir4(00)i2-Al2Cl6 system. The Lewis acid treated materials
were found to exhibit approximately two order of magnitude greater
activity than the iridium clusters deposited on alumina. The high
selectivity for the formation of methyl chloride in the supported
system is attributed to the presence of the HC1 in the reactant
gases which would convert C3 intermediates to methyl chloride prior
to homologation and hydrogenation.
In the homogeneous system IrCl(00)3 was also preposed to be an
active catalyst or catalyst precursor.6 Investigation of this
supported mononuclear complex both in the absence and presence of
aluminum chloride resulted in the formation of only minor amounts of
methyl chloride upon reaction with H2, CD and HC1. The formation of
methyl chloride has also been previously reported from the reaction
of H2, 00 and HC1 over supported metallic iridium.40 The
investigation of metallic iridium as a catalyst for the reduction of
carbon monoxide to methyl chloride resulted in only trace amounts of
methyl chloride below 200C in a stagnant reactor while above 200C
the activity was observed to increase. It is proposed that metallic
iridium is not responsible for the observed formation of methyl
chloride in the supported Ir4 (00) 12-A12C16 system and that
stabilization of a discrete iridium complex active for methyl
chloride formation occurs.
The supported iridium clusters were investigated by infrared
spectroscopy after reaction with H2, 00 and HC1. The materials
investigated were no longer active for reduction of carbon monoxide.
Iridium carbonyl on alumina or silica gel is proposed to decompose


78
to mononuclear iridium chlorocarbonyl complexes as indicated by
infrared data. A decarbonylation reaction whereby interaction of
the bound carbonyl groups of the cluster may interact with hydroxyl
groups cxi the surface of the support is believed to result in
decomposition of the cluster. Infrared investigation of the
aluminum chloride treated iridium clusters after reaction revealed
complex spectra which are attributed to the presence of stabilized
multinuclear and not metallic iridium. Similar complex infrared
data was obtained in the previously studied46 phosphine substituted
clusters which were proposed to be multinuclear iridium
chlorocarbonyl species. Ihe decomposition of supported Ir4(00)12-
A12C16 via interaction with surface A1C12 grcxps formed upon
treatment with aluminum chloride and the presence of small amounts
of iridium metal undetected by infrared spectroscopy cannot be ruled
out.
In the phosphine substituted and the aluminum chloride treated
iridium carbonyl systems data suggest that catalytic reduction of
carbon monoxide is not the major pathway which would account for the
formation of methyl chloride. Discarding the presence of organic
residues in the supported systems the major route for the formation
of methyl chloride appears to be one comprising of the decomposition
of the carbonyl groups originally present on the lr4(00)12 clusters.
The inability to form and stabilize an active heterogeneous analog
of the homogeneous Ir4 (CD) 12-A12C16 system from lr4(00)12 or
IrCl(00)3 suggests that alterations of the active environments have
occurred in the heterogenized system during catalysis.


III. RHODIUM PERFLUOROGARBOXYIATE
TRIHffiNYLFHOSFHINE OCMPLEXES PC
OIEFIN HYEROPOFMYIATIC
A. Background
Metal carboxylate dimers have been the subject of many
reviews.80-82 The investigation of these complexes is of interest
since they can act as model compounds for the study of metal
synergism. These dinuclear complexes contain metal-metal bonds and
four bridging carboxylate ligands resulting in a "lantern
structure." Rhodium(II) carboxylates of the general formula
Rh2(2CR)4/ possess a rhodium-rhodium single bond and readily form
adducts, in which the axial positions are occupied by solvents or
ligands.
The reactivity of rhodium (II) carboxylates with a variety of
donor ligands has been widely investigated.83-89 Drago and
coworkers have measured equilibrium constants and enthalpy of
coordination for various axial ligands.8386 The formation of 1:1
and 2:1 ligand to dimer complexes has been observed. Once the 1:1
adduct has been formed, the second axial ligand is less strongly
bound at the second rhodium center.84 Studies have established that
electron withdrawal front rhodium (II) perfluorocarboxylate complexes
enhances the Lewis acidity of the axial coordination sites. Fully
fluorinated rhodium (II) tetrakis (heptafluorobutyrate) has greater
79


80
covalent and electrostatic sigma acceptor properties than the
corresponding butyrate complex. Research has also focused on the
influence of base coordination at one rhodium center on the
stretching frequency of coordinated CD at the second metal center.85
The coordination chemistry of rhodium (II) carboxylates has also
been extended to include olefins. Spectroscopic studies conducted
by Doyle et al. yielded the first demonstration of olefin
coordination with rhodium(II) perfluorocarboxylate complexes.87
Equilibrium constants were reported for the 1:1 adducts of
Rh2(O2OCF3)4 with a series of alkenes. No spectroscopic evidence
for the binding of alkenes by rhodium (II) acetate in solution was
obtained in Doyle's study. These results are in contrast to those
reported by Schurig where equilibrium constants for olefin-
rhodium (II) acetate adducts have been determined from retention data
by ccnplexation gas chromatography rather than from spectroscopic
studies.88
The olefin coordination chemistry of rhodium (II)
perfluorocarboxylates in solution has been extended by Doyle et al.
to include rhodium(II) tetrakis (heptafluorcbutyrate).89 Equilibrium
constants for 1:1 complexes between rhodium (II) perfluorobutyrate
are approximately three times greater than those determined for
rhodium (II) trifluoroacetate. The increased ability of the
fluorinated rhodium (II) carboxylates to coordinate molecules is
attributed to the increased Lewis acidity of the rhodium center due
to the electron-withdrawing properties of the fluorinated
carboxylate ligands. Based upon these findings, rhodium


81
carbaxy lates would be expected to exhibit activity in catalytic
reactions involving the binding and subsequent activation of
molecules such as olefins, carbon monoxide, etc.
Rhodium(II) acetate has been reported to be an active catalyst
for the homogeneous hydrogenation of olefins in a wide variety of
solvents.90'91 A mechanism has been proposed which involves the
intact dimer and heterolytic cleavage of dihydrogen92 as shown below
in Equation 3-1. Terminal olefins have been shewn to undergo 15-20%
+H2 +l
Rh2 (QAc) 4 > HEh(QAc) 3Rh >
HOAc (3-1)
(HL)Rh(QAc) 3Rh > H2L + Rh2 (QAc) 4
isomerization vhile the catalyst is less active or inactive for
internal olefins.
The cyclopropanation of diazoesters to alkenes to yield
cyclcpropanes has also been reported to most effectively be
catalyzed by rhodium (II) carboxylates93'94 as shewn in Equation
3-2. The cyclopropane carboxylic acid ester products have use as
v1 /
crc
/ \
r3
R2 R4
R1 R3
Rh2 (C^CR) 4 \ /
+ No = CH-OOOR > C C
/\/\
r2 c R4
/ \
H OX)R
(3-2)


82
insecticides. Mechanistically, a Rh2 (O2CR) 4-carbene complex is
proposed which then transfers the carbene to the substrate.95 In
the presence of rhodium(II) carboxylates and vanadium or molybdenum
compounds cyclohexene can be oxidized to give 1,2 epoxycyclohexene-
3-ol.96 The reaction takes place at 55C under 1 atm. of oxygen and
proceeds via a cyclohexyl hydroperoxide intermediate. Ihe best
results have been reported for fluorinated carboxylate ligands such
as trifluoroacetate.97 Rhodium(II) carboxylates react in methanolic
HBF4 in the presence of triphenylphosphine and lithium carboxylate
to produce Rh^CR) (PEh3)3.98 These complexes have been reported to
catalyze the homogeneous hydrogenation of alkenes and alkynes.
Rhodium(II) carboxylates have received attention as second
generation platinum metal anticancer compounds. Ihe use of these
complexes was first reported by Bear in 1972.99 Investigation into
the chemical properties and biological effects of rhodium (II)
carboxylates in relationship to their ability to bind unprotonated
amino and sulphydryl groups have been conducted. Invivo studies
have shewn that rhodium carboxylates are able to inhibit certain
biological processes in particular the cellular synthesis of DNA
While these complexes have been studied as catalysts for some
reactions as discussed above, the fluorinated dimers have not been
extensively investigated. Ihe reported increased ability of the
fluorinated rhodium carboxylates to bind molecules such as olefins
and 00 would be expected to render these complexes active catalysts
for reactions such as hydrof ormylations.


83
Hie hydroformylation reaction was discovered by 0. Roelen in
1938 while studying the effect of added olefins in the Fischer-
Tropsch Process.100 Later studies concluded that the presence of
cobalt in the heterogeneous Fischer Tropsch catalyst was catalyzing
the hydroformylation reaction and that the actual catalyst was
homogeneous.101 The hydroformylation or oxo" reaction is the
reaction of synthesis gas with an olefin102 as shown in Equation
3-3. In the absence of a catalyst the reaction does not proceed.
catalyst
H2 + 00 + RCH CH2 > RCH2CH2CHO + RCH(CH0)CH3
(3-3)
The products from the hydroformylation reaction are aldehydes. Both
the linear and branched aldehyde may be formed. Linear aldehydes
have the greatest chemical utility. The addition of bulky phosphine
ligands to hydroformylation catalysts results in an increase in the
selectivity for the formation of the linear aldehyde. Byproducts
commonly formed during hydroformylations include alkanes and
alcohols.
Bie production of butyraldehyde from the reaction of H2, CO and
propylene is the largest commercial application of the
hydroformylation process.103 Approximately 6 billion pounds of
butyraldehyde are produced annually. Bie condensation arid
hydrogenation of the aldehydes ultimately yields alcohols which are
used as ccnpanerrts of plasticizers. An additional 2-6 billion
pounds of other aldehydes are also produced annually by the
hydroformylation process. The ultimate products are long chain


84
alcohols which have application in the production of biodegradable
soaps, detergents, and as components of plasticizers.
Two aspects of the hydroformylation reaction are of industrial
importance. One involves the formation of undesirable byproducts
which should be minimized during reaction. The other aspect
concerns the development of processes which avoid expensive
operating conditions which occur when high pressures and
temperatures are employed to carry out the reaction. Commercial
processes have been developed based upen both cobalt and rhodium
catalysts with each having their own advantages and
disadvantages.104
Cobalt hydroformylation processes typically employ dicobalt
octacarbonyl, Co2(00)8, as the catalyst precursor.105 The active
catalyst is HCo(00)4 which is a volatile, unstable complex that is
difficult to separate from the reaction products and recycle into
the system. Processes based upon hydrido cobalt catalysts typically
operate under severe reaction conditions. Reaction pressures of
200-350 atmospheres and temperatures between 150-200C are generally
employed. The product isomer ratio obtained with hydrido cobalt
catalysts is approximately 3 or 4:1 (mol linear : mol branched
aldehyde product). The high reaction pressures and temperatures
used to stabilize these complexes promote the formation of
byproducts.
Fhosphine modified hydrido cobalt catalysts have also been
developed for the hydroformylation of olefins.106 These systems
usually result in the complete reduction of the aldehyde to the


85
alcohol. The phosphine used is tributylphosphine and the active
catalytic species is proposed to be HCo(OO)3(PBu3). The phosphine
modified system is less active for hydroformylation but much more
active for hydrogenation and generally results in a linear :
branched alcohol ratio of 7:1. This catalyst is more stable than
the unmodified catalysts resulting in lower reaction pressures of
100 atmospheres.
Ccnmercial hydroformylation processes have recently been
developed based upen rhodium.107 Much milder reaction conditions
are used with the rhodium systems compared to any of the cobalt
systems and rhodium has an activity 104 times greater than that of
cobalt. Reaction pressures of 10-25 atmospheres and temperatures
around 100C are generally employed. Ehosphine modified hydrido
rhodium ccxrplexes, such RhH(OO) (FEh3)3,108'109 are used as
catalysts. Excess triphenylphosphine is added to increase the
product selectivity for the formation of the linear aldehyde while
decreasing the rate of hydroformylation. The reaction has even been
conducted in molten triphenylphosphine.110 Despite the high
activity and selectivity and milder reaction conditions employed
with modified rhodium catalysts, the high cost of rhodium and
recovery problems has limited their use. The development of
homogeneous rhodium systems or heterogeneous systems which exhibit
greater activity and selectivity than those currently employed and
operate under milder reaction conditions may offset seme of the
disadvantages associated with current rhodium systems.


Full Text

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81,9(56,7< 2) )/25,'$


SYNTHESIS GAS TRANSFORMATIONS WITH HETEROGENEOUS
IRIDIUM AND HOMOGENEOUS RHODIUM METAL COMPLEXES
BY
CINDY S. GETTY
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
1988
¡0 OF £ LIBRARIES

To My Parents

ACKNOWLEDGMENTS
This research and dissertation would not have been possible
without the support, encouragement and guidance of a number of
people. First I would like to thank my mentor, Russell S. Drago and
his wife, Ruth. Had it not been for Doc's "idears" and skill on the
tennis courts, my stay at the University of Florida would not have
been as well-rounded and fulfilling. He always knew I enjoyed a
good argument. Ruth also deserves a special thanks for making me
feel as if Florida was a second heme.
The entire Drago group has also influenced my graduate studies.
A few members have played a special role. I would like to thank Dr.
Keith Weiss, Larry "Chmoo" Chamusco, Jerry "Bear" Grünewald, Thomas
"Them" Cundari, Ngai "Nagy" Wong and my brother Alan "Hard Body"
Goldstein. To Mark "Sparticus" Barnes, I ewe a special thanks for
his friendship which I will always cherish. Dr. Roy King, of the
Microanalytical Laboratories, also deserves a special thanks for all
of his help.
During my undergraduate days at S.U.N.Y. Plattsburgh my studies
in chemistry were greatly influenced by Dr. Gerald F. Kbkoszka.
Without his encouragement I might not be pursuing a career as a
chemist.
iii

Finally, for all of their support and love over the years I
would like to thank my entire family and especially my husband and
best friend, Ed. I always imagined graduate school as a time for
total devotion to one's studies and development as a chemist. Ed
has taught me that there is more to life than chemistry. For this I
am forever indebted to him.
iv

TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
LIST OF TABLES ix
LUST OF FIGURES X
ABSTRACT xiii
CHAPTER
I. INTRODUCTION 1
II. INVESTIGATION OF SUPPORTED IRIDIUM CARBONYL FOR THE
TRANSFORMATION OF SYN GAS AND HC1 TO METHYL
CHLORIDE 3
A. Background 3
B. Experimental 18
Materials 18
Instrumentation 19
Fixed Bed Flew Reactor 20
Preparation of a Phosphinated Support 23
Preparation of the Supported Triphosphine
Substituted Iridium Carbonyl Clusters 24
Preparation of Directly Deposited Tetrairidium
Carbonyl Clusters on the Support 24
Preparation of the Aluminum Chloride Tetrairidium
Carbonyl Cluster Treated Supports 25
Preparation of Other Lewis Acid Deposited
Tetrairidium Carbonyl Clusters 26
Preparation of Aluminum Chloride Treated
Commercial Methanol Catalysts 26
v

Reaction of the Supports and the Supported
Metal Complexes with Carbon Monoxide, Hydrogen
HCl(g) 27
C. Results and Discussion 27
Reinvestigation of Earlier Work of the Supported
Phosphine Substituted Tetrairidium Carbonyl
Cluster 27
Investigation of Directly Deposited Ir4 (00) 12 39
Investigation of Supported lr4(00)12 for Catalytic
Activity Upon Reaction with H2, 00 and HCl(g).... 44
Investigation of the Aluminum Chloride Treated
Deposited Iridium Carbonyl Clusters 47
Investigation of the Aluminum Chloride Treated
Supported Iridium Carbonyl Clusters for Catalytic
Activity Upon Reaction with H2, 00 and HC1 (g) 51
Comparison with the Homogeneous lr4(00)i2-A12C16
System 53
Infrared Investigation of Deposited lr4(C0)12
After Reaction with H2, 00 and HC1 (g) 55
Infrared Investigation of Supported
Ir¿ (CO) i o-AloClc Complexes After Reaction with
H2, 00 and HCl(g) 58
Investigation of Supported IrCl(00)3 Upon Reaction
with H2, 00 and HCl(g) 63
Investigation of Metallic Iridium Upon Reaction
with H2, 00 and HCl(g) 67
Investigation of Other Lewis Acids 68
Investigation of A12C16 Treated Commercial 00
Reduction Catalysts 69
Mechanism Proposed for the Formation of Methyl
Chloride 71
D. Summary 75
vi

III. RHODIUM PERFUÃœOROCARBOXYIATE TRIfflENYIfHOSFHINE
COMPLEXES POR OIEFIN HYEROFORMYIATIOi 79
A. Background 79
B. Experimental 88
Reagents 88
Instrumentation 89
Synthesis of Tetrakis (acetato) Dirhodium (II) 90
Synthesis of Tetrakis(perfluorobutyrato)
Dirhodium(II) 92
Synthesis of Other Rhodium(II) Carboxylate Dimers. 92
Preparation of Trifluoroacetato
Tris (triphenylphosphine) Rhodium(I) 93
Preparation of Trifluoroacetato
Tris (triphenylphosphine) Rhodium(I) from Hydrido
Tetrakis (triphenylphosphine) Rhodium (I) 93
Preparation of Trifluoroacetato
Bis (triphenylphosphine) Rhodium(I) Carbonyl 94
Preparation of Nafion Supported Rh(02CCF3) (PPh3) 3- 94
Hydroformylation of Olefins with the Rhodium
Complexes 95
C. Results and Discussion 95
Investigation of Rhodium (II) Perfluorocarboxylate
Complexes as Catalysts for Hydroformylation of
1-Hexene 95
Effect of Added Triphenylphosphine on Catalytic
Activity and Selectivity 100
Comparative Studies with Other Rhodium Carboxylate
Complexes 104
Comparative Studies with Rhodium(I) Complexes 107
Investigation of the Rhodium Perfluorocarboxylate
Triphenylphosphine Catalyst System During
Hydroformylation 108
vii

Visible Investigation on the Effect of Added
Olefin and Phosphine to the Rhodium (II)
Perfluorobutyrate Complex 120
Investigation of the Species Formed Upon Reaction
of Rhodium(II) Perfluorocarboxylate Complexes
with Triphenylphosphine 121
Investigation of Rh(02CCF3) (PFh3)3 for Catalytic
Hydroformylation of 1-Hexene 133
Investigation of the Rh(0?CCFo) (Pih-i) -> System
During Reaction 134
Investigation of Trifluoroacetate Carbonyl
Bis (triphenylphosphine) Rhodium(I) 139
Comparative Hydroformylation Studies with Hydrido
Carbonyl Tris (triphenylphosphine) Rhodium(I) 140
Preparation of [Rh(FFh3)3]+[ (020CF3) ]“ Exchanged
onto Ñafien 145
Hydroformylation of 1-Hexene using the Polymer
Supported Rhodium Catalyst 147
Leaching of the Catalyst from the Resin 150
Hydroformylation of Propylene Using
Tris (triphenylphosphine) Rhodium(I) Incorporated
in a Polymeric Membrane Film 150
Hydroformylation of Other Olefins with
Rh(02CCF3) (PEh3)3 151
Hydrogenation of 1-Hexene and Other Miscellaneous
Reactions of CO, H2 and Heptaldehyde with
Rh(02CCF3) (PFh3)3 154
Proponed Mechanism for the Catalytic
Hydroformylation of 1-Hexene with
Rh(02CCF3) (FFh3)3 and Added Triphenylphosphine... 159
D. Summary 162
IV. CONCLUSION 166
REFERENCES 171
BIOGRAPHICAL SKETCH 179
viii

LIST OF TABLES
Table Page
2-1 Ways to Utilize Clusters in Catalysis 5
2-2 Advantages of Homogeneous Versus Heterogeneous
catalysts 8
2-3 Possible Reactions and the Thermodynamic
Feasibility for the Formation of Methyl Chloride. 12
2-4 Major Carbonyl Bands in the Infrared Spectra for
Phosphine Substituted Ir^OO)^ and Ir4(ao)12.... 29
2-5 Control Reactions for the Fhosphine Substituted
Supported System 31
2-6 Major Carbonyl Bands in the Infrared Spectra for
Fhosphine Substituted Ir4(CO)12 and Ir4(00)i2
After Reaction with H2, CO and HC1 57
3-1 Phosphorus NMR Data for the Rhodium
Ferfluorocarboxylate Complexes 112
3-2 Fluorine NMR Data for the Rhodium
Fterfluorocarboxylate Complexes 115
3-3 Infrared Data for the Rhodium
Ferfluorocarboxylate Complexes 118
3-4 Comparison of 1-Hexene Hydroformylation Activity
for Various Rhodium(I) Catalysts. 135

LIST OF FIGURES
Figure Page
2-1 A Proposed Mechanism For the Formation of Methyl
Chloride with the Phosphine Substituted Supported
Iridium Clusters 17
2-2 A Diagram of the Fixed Bed Flew Reactor 22
2-3 Structure of the Ethoxy Surface Species Formed
During Functionalization of the Alumina Oxide 34
2-4 Schematic Representation of the Decomposition of the
Ethoxy Groups at Elevated Temperatures 37
2-5 Infrared Spectra of lr4(00)12 Deposited onto Alumina
Before and After Treatment with A12C16 41
2-6 Infrared Spectra of Ir4(00) 22 Deposited onto Silica
Gel Before and After Treatment with A12C16 42
2-7 A Sample Gas Chromatograph of the Products Formed
Upon Reaction of H2, 00 and HC1 over the Supported
Iridium Clusters at 125°C and 1 Atmosphere 45
2-8 Activity Curves for the Various Supported Iridium
Carbonyl Clusters for the Formation of Methyl
Chloride 46
2-9 Infrared Spectra of lr4(00)^2 Deposited onto Alumina
and Silica Gel After Reaction with H2, 00 and HC1 at
125°C 56
2-10 Infrared Spectrum of Al203/Ir4(00)12/Al2Cl6 After
Reaction with H2, 00 and HC1 at 125°C 60
2-11 Infrared Spectrum of SiO^I^ (00) 12/A12C16 After
Reaction with H2, 00 and HC1 at 125°C 61
2-12 ESCA of SiO^I^ (00) 12/A12C16 Before and After Reaction
with H2, 00 and HCl at 125°C 62
2-13 Infrared Spectra of Al203/TrCl (00) 3 Before and After
Reaction with H2, 00 and HCl at 125°^ 64
x

Fioure
Page
2-14
Infrared Spectra of Al2C>3/IrCl (00) 3/Al2Cl6 Before and
After Reaction with H2, 00 and HCl at 125°C
66
2-15
Proposed Mechanism for the Formation of Methyl Chloride
with the Supported Iridium Carbonyl Clusters
72
3-1
A Diagram of the Pressure Bottle Apparatus Used for the
Hydroformylation Reactions
91
3-2
A Sample Gas Chrxanatograph of the Products Formed After
the Hydroformylation of 1-Hexene with the Rhodium (II)
Perfluorocarboxylate Catalyst at 100°C
97
3-3
A Sample Mass Spectra of the Solution After Reaction
Enriched with ^Carbon Monoxide
99
3-4
Activity Curves for the Formation of Heptaldehyde with
Varying Ratios of Rhodium (II) Ferfluorobutyrate to
Triphenylphosphine
101
3-5
Bar Graphs Illustrating the Effect of Added Triphenyl¬
phosphine on Iscmer Ratio
103
3-6
Comparative Activity Curves for the Hydroformylation of
1-Hexene with Rhodium (II) Ferfluorobutyrate and
Rhodium (II) Trifluoroacetate with Added Phosphine
105
3-7
Color Changes Observed During Reaction
109
3-8
31P NMR Spectrum of the Reaction Mixture During
Hydroformylation with Rh2(020C3F7)4 and 5PFh3
111
3-9
19F NMR Spectrum of the Reaction Mixture During
Hydroformylation with Rh2(020C3F7)4 and 5PEh3
114
3-10
Infrared Spectrum of the Reaction Mixture During
Hydroformylation with Rh2 (020C3F7) 4 and 5PFh3
117
3-11
Visible Spectral Overlay Upon Sequential Addition of
1-Hexene to Rhodium (II) Ferfluorobutyrate
121
3-12
Visible Spectral Overlay Upon Sequential Addition of
Triphenylphosphine to Rhodium(II) Ferfluorobutyrate...
123
3-13
Infrared Spectrum of Rh(02CCF3) (PPh3)3
127
3-14
19F NMR Spectrum of Rh(02CCF3) (PPh3)3
129
3-15
31P NMR Spectrum of Rh(02CCF3) (PEh3)3
132
xi

Page
Figure
3-16 Infrared Spectrum of the Reaction Mixture During
Hydroformylation of 1-Hexene with Rh^CCT^) (Pih3)3... 138
3-17 31P NMR Spectrum of the Reaction Mixture During
Hydroformylation of 1-Hexene with Rh(02CCF3) (PPh3)3... 142
3-18 Bar Graph Comparison of the Hydroformylation Activity
of Rh(C>2CCF3) (PHi3)3 Versus RhH(OO) (FEh3)3 143
3-19 Bar Graph Comparison of the Homogeneous Versus the
Heterogeneous Hydroformylation System 149
3-20 A Sample Mass Spectrum of the Reaction Solution After
Hydroformylation of Styrene 153
3-21 A Sample Mass Spectrum of the Reaction Solution After
Hydroformylation of Ethyl Vinyl Ether 156
3-22 Proposed Mechanism for the Hydroformylation of Olefins
with the Tris(tripherylphosphine) Rhodium(I)
Trifluoroaoetate System 160
xii

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 Fhiloscphy.
SYNTHESIS GAS TRANSFORMATIONS WITH HETEROGENEOUS
IRIDIUM AND HCMDGENEOUS RHODIUM METAL COMPLEXES
By
Cindy S. Getty
December 1988
Chairman: Russell S. Drago
Major Department: Chemistry
There has been a great deal of interest in the development of
chemicals from synthesis gas (H2 and 00). Typically, the reactions
are catalyzed by soluble (homogeneous) metal complexes or supported
(heterogeneous) metal complexes or metal particles. The emphasis of
this work has been on the development of homogeneous and
heterogeneous catalytic systems capable of the indirect
transformation of H2 and 00 into chemicals under mild reaction
conditions.
Supported iridium carbonyl and aluminum chloride were
investigated in an attempt to heterogenize an analogous homogeneous
catalyst. The presence of aluminum chloride was found to lead to
cluster interactions resulting in a system capable of selective
reduction of carbon monoxide under mild reaction conditions. When a
gaseous mixture of H2, CD and HC1 was passed over the supported
cluster at 125°C, methyl chloride, methane, carbon dioxide and water
xiii

were observed as major products. Unlike the homogeneous analog only
trace C2 products were detected. Infrared spectroscopy was used to
investigate the preparation of the deposited clusters as well as the
iridium species formed on the support during reaction.
The second study involved the investigation of a rhodium
carboxylate triphenylphosphine complex which was found to be an
active, homogeneous hydroforrnylation catalyst. The system
selectively produced more of the linear aldehyde than the branched.
The product selectivity was found to depend upon the amount of
phosphine present. Spectroscopic studies supported that a
bis (triphenylphosphine) rhodium (I) trifluoroacetate carbonyl species
was the active catalyst. Comparative studies with other rhodium
carboxylate complexes and hydroforrnylation catalysts shewed that the
perfluorocarboxylate complexes exhibited greater activity.
xiv

I. INTRODUCTIOÍ
The investigation of fuel sources other than oil has been of
interest since the 1970s. An attractive alternative is coal. The
combustion of coal results in the formation of a gaseous mixture of
hydrogen and carbon monoxide referred as synthesis gas. Synthesis
gas nay be used as a feedstock for the production of chemicals and
fuels.1
A large number of chemicals may be directly or indirectly
produced from synthesis gas.2 In direct processes, no molecules
other than carbon monoxide and hydrogen are employed as the
reactants. An indirect process would involve the combination of
carbon monoxide and hydrogen with a third reactant molecule. The
reactant molecule may be an olefin, alcohol, HC1, etc.
Transition metal complexes are generally employed as catalysts
for the conversion of synthesis gas into chemicals.3'4 Typically,
the catalysts are soluble (homogeneous) metal complexes or supported
(heterogeneous) metal complexes or metal particles. Investigation
of the activity and stability of metal complexes that catalyze the
transformation of synthesis gas under mild reaction conditions is of
interest. Reported here are the results of two studies involving
the investigation of transition metal complexes as catalysts for the
1

2
indirect transformation of synthesis gas into chemicals. The first
study involves the investigation of supported iridium carbonyl
clusters as catalysts for the reaction of H2, 00 and HC1 under mild
reaction temperatures and pressures to selectively produce methyl
chloride. The development of a catalytic system for the formation
of methyl chloride based upon synthesis gas would be industrially
attractive. The iridium complexes were studied in an attempt to
heterogenize a homogeneous iridium system reported to produce minor
amounts of methyl chloride during the hydrogenation of carbon
monoxide.5'6 This study allows for a direct comparison to be made
on a system employing a metal ccnplex of well-defined composition
and nuclearity. The stability of the metal clusters when supported,
as well as under conditions employed during catalysis, was also
probed. Infrared spectroscopy was used to investigate the
preparation of the deposited clusters and the iridium species formed
during reaction with hydrogen, carbon monoxide, and HC1.
The second study involves the investigation of a homogeneous
rhodium carboxylate system as a catalyst for the hydroformylation of
olefins. The ability to vary the carboxylate ligands on the rhodium
complex allows for comparisons to be made of the activities of such
systems during catalysis. The effect of added phosphine on the
distribution of reaction products and the stability of the system
was also studied by a variety of spectroscopic techniques. Finally,
comparative studies with commonly employed hydroformylation
catalysts allow for investigation of the industrial potential of the
rhodium carboxylate system.

II. INVESTIGATION OF SUPPORTED IRIDIUM CARBONYL FOR THE
TRANSFORMATION OF SYN GAS AND HC1 TO METHYL CHLORIDE
A. Background
For over a decade there has been a growing interest in the use
of coal as a potential source of chemical feedstocks and fuels.
Such interest was triggered by rising oil prices in the early 1970s
as well as by a growing concern about the eventual depletion of our
oil resources. Unfortunately, coal cannot be directly converted
into fuels. The combustion of coal in the presence of steam results
in the formation of a gaseous mixture of hydrogen and carbon
monoxide7 as shewn in Equation 2-1. This gaseous mixture
H20(1)
C(coal) > 00(g) + H2(g) Hrxn = +176 KJ/mol (2-1)
is referred to as synthesis gas because synthesis gas and not coal
can be converted into chemical feedstocks and fuels in the presence
of a catalyst. Many articles have focused on the use of synthesis
gas as a raw material for industrial chemicals.2'8-11
One of the best known and oldest processes utilizing synthesis
gas to produce gasoline is the Fischer-Tropsch Process.12 This
process employs a heterogeneous metal catalyst containing Fe, Ru or
3

4
Co metal dispersed on a support such as alumina or silica gel as
shewn in Equation 2-2. Depending upon the catalyst and reaction
conditions the products are hydrocarbons, oxygenates or mixtures
thereof.13 A myriad of products are formed in the Fischer-Tropsch
Fe,Ru,Co Hydrocarbon
n(00 + H2) > and (2-2)
Oxygenated Products
Process. The molecular weight distribution of the products is
characteristic of polymerization reactions. The products follow a
Schulz-Flory distribution function such that the probability of
chain growth is related to the rate of chain propagation and chain
transfer.13
Currently, the only large commercial Fischer-Tropsch facility
for the production of gasoline, gas oil and paraffins from coal is
located in Sasolburg, South Africa, where large deposits of coal
resources exist.14 Typical working conditions are 25 atm. at 220-
240°C employing an extruded iron catalyst. The wide product
distribution and the lack of economically mined coal deposits have
deterred the use of the Fischer-Tropsch Process elsewhere in the
world.
Research objectives in the area of synthesis gas conversion
have focused on the development of transition metal catalysts
exhibiting high selectivities for the formation of either oxygenated
products15 or lew molecular weight unsaturated hydrocarbons.16 The
use of metal carbonyl clusters as catalysts or catalyst precursors
has been the subject of many reviews.17”20 Because of their well-

5
defined composition and nuclearity these clusters may form the basis
for a new generation of highly selective catalysts or catalyst
precursors in reactions such as hydroformylation, hydrogenation,
isomerization, 00 reduction, etc. In clusters, the metal sites are
also subjected to electronic influences of the surrounding ligands
on the metal framework. Analogies between metal carbonyl clusters
and metal surfaces covered with carbon monoxide have been
suggested.18'21'22
There are many advantages for using clusters rather than
mononuclear ocrplexes as catalysts.23'24 The multinuclear nature of
clusters allows 00 and hydrogen to be bonded in neighboring
positions allowing for interaction between metal atoms. In clusters
there are also a number of metal sites available for the bonding of
carbon monoxide. Metal sites in clusters may also be influenced by
electronic changes around the metal framework resulting from
addition of ligands. Shown below in Table 2-1 are the ways of
utilizing clusters in catalysis.17
Table 2-1. Ways to Utilize Clusters in Catalysis.
Homogeneous Heterogenized Heterogenized
Intact Intact Clusters Cluster-Derived
Clusters in > Anchored or Deposited > Metal Particles on
Solution on Oxide Supports Oxide Supports
Homogeneous systems employing metal carbonyl clusters as
catalysts or catalyst precursors exhibit high selectivity for the
formation of oxygenated products such as methanol, ethanol and

6
ethylene glycol and operate under extreme pressure conditions (>1000
atm.). Metal carbonyl clusters such as Ru3(00)12,25 Rh^CD) 1626 and
CO2(00)827 have been used as catalysts for the homogeneous
hydrogenation of carbon monoxide as shown in Equation 2-3.
Ru, Rh, Co
H2 + 00 > CH3CH + C2H5OH + (CH2OH)2 (2-3)
T= 200-300°C
The product selectivity observed in these homogeneous systems is
dependent upon a number of factors15 including the reaction
temperature and pressure, solvent characteristics, presence of
specific ligands and the use of promoters. The major disadvantage
with homogeneous catalysts involves the difficulty of separating the
catalyst from the product.
Heterogeneous systems using metal carbonyl clusters as
catalysts or catalyst precursors tend to produce hydrocarbon
products such as alkanes and alkenes. The use of metal carbonyl
clusters as catalysts is very attractive in view of recent reports
in the literature indicating that metal particle size has a
significant effect on the selectivity for <30 hydrogenation.28'29 It
is believed that small metal particles lead to the formation of low
molecular weight hydrocarbon products such as ethane and ethylene.
Once aggregation of these metal particles occurs the formation of
higher molecular weight products similar to those observed in
typical Fischer-Trcpsch synthesis is observed.30 Understanding the
reactivity of the cluster with the support is essential to

7
controlling metcLI particle size and determining the chemical
transformations that occur on the way to forming an active catalyst.
When Ru3(00)12 is supported on alumina no oxygenated products
are detected upon reaction with H2 and CD and the formation of Ru
metal is observed31 as shewn in Equation 2-4. The formation of
oxygenated products was observed when Ru3(CD)12 supported onto a
basic support such as magnesia as shewn in Equation 2-5. After
catalysis the presence of an anionic cluster, [RugC(CD)16]“2 was
identified. The oxygenated selectivity for ruthenium carbonyl
supported on magnesia was suggested to be a result of the presence
of an intact metal carbonyl cluster on the surface.
^3 (°°) 12/a12°3
Ho + 00 > CH4 + Cp-Cm Hydrocarbons (2-4)
200-350°C, 21atm.
Ru3 (00) 12/MgO Oxygenates (CH30H + C2H50H)
Hp + 00 > CH4 + Cp-C-in Hydrocarbons (2-5)
200-350°C, 21atm.
There have been two approaches used for the development of
catalytic materials from meted carbonyl clusters. One involves
supporting the metal complex such that an intact cluster framework
with the ligands still bound to it is maintained. This type of
catalyst resembles a homogeneous catalyst. A second method is to
decompose the cluster to a metal particle where the particle size
distribution can be controlled by the cluster decomposition. The
first approach allows a better understanding of the material because
techniques such as infrared spectroscopy are available for studying

8
metal carbonyl carpi exes. The stability of these intact cluster
catalysts under reaction conditions is often questioned.
A goal of researchers has been to develop heterogenized
homogeneous catalysts or "hybrid catalysts".32 In the development
of hybrid catalysts the presence of an intact supported metal
ocrplex is desireable. By developing such systems many of the
advantages of both homogeneous and heterogeneous catalysts could be
retained. A listing of the advantages of homogeneous and
heterogeneous catalysts is found in Table 2-2. A hybrid catalyst
should exhibit high selectivity and activity as well as exhibit high
thermal stability and ease of product separation.
Heterogenizing metal carbonyl clusters has been the subject of
many reviews.17»33'34 The main routes used to support metal
clusters include: (1) direct surface bonding or physisorption with
an inorganic oxide support; (2) anchoring of the cluster on
functionalized inorganic oxides and (3) entrapment in zeolites.
Table 2-2. Advantages of Homogeneous Versus Heterogeneous
Catalysts
Homogeneous
versus
Heterogeneous
1.more active due to
availability of metal
1. separation of catalyst
from product
2. reproducible
2.minimizes reactor corrosion
3.electronic and steric
properties can be varied
3. high thermal and mechanical
stability
4.more selective

9
The Inmobilization of metal carbonyl clusters has been achieved
by surface bonding or deposition onto inorganic oxide supports. In
seme cases interaction of the cluster with the oxide support has
been established. Ionic and covalent bonding of the cluster with
the support can be employed. Ionic bonding occurs from nucleophilic
attack of a surface hydroxyl group on a CD ligand of the cluster.
Covalent bonding occurs from oxidative-addition of a surface
hydroxyl group with one of the metal-metal bonds of the cluster.
Fhysisorption of the cluster onto the inorganic oxide has also been
shewn to occur. In these systems intact metal carbonyl clusters
have been shewn to be present. The clusters may undergo interaction
with sites present on the support. Ihe type of bonding of a cluster
onto an oxide support is believed to be dependent upon the nature of
the support and its pretreatment.35
Ihe use of a chemically modified support is an alternative
method of anchoring a cluster onto a support. The recent literature
contains many examples of silica and alumina supports that have been
functionalized with reagents of the general formula
(C2H5O) 3Si (CH2) n* where X is a donor group capable of coordinating
to metal complexes.36'37 In general two methods of preparation have
been used to anchor clusters onto oxide supports. The first
involves anchoring the cluster via ligand exchange to a
functionalized support. The other method involves preparing a metal
complex bound to a linking agent followed by coupling to an
inorganic oxide surface. These two methods are depicted below in
Equations 2-6 and 2-7.

10
f-0-Si-CH2CH2X > 4“0-Si“CH2CH2M%£n_1 (2-6)
f<3H
(OR) 3-Si-CH2CH2XMmITl_1 > ^-0-Si-CH2CH2XMnItl_1 (2-7)
In 1981, Muetterties and ccworkers5 discovered a novel
homogeneous system that catalyzed the conversion of carbon monoxide
and hydrogen into light hydrocarbons (primarily ethane) under very
mild reaction conditions as shewn in Equation 2-8. The catalyst was
Ir4 (CD) Y2 in a molten Al2Cl6-NaCl medium.
There are some significant results from this homogeneous
reaction. The formation of hydrocarbon products was observed with
no oxygenated products detected. Recall that homogeneous systems
containing meted, carbonyl clusters as catalysts or catalyst
precursors typically produce oxygenated products from reaction of
carbon monoxide with hydrogen. The reduction of carbon monoxide
also occurred under very mild reaction conditions of 1-2 atmospheres
pressure and temperatures below 200°C. The mild reaction conditions
necessary for the reduction of carbon monoxide in the homogeneous
Ir4(00)12/Al2Cl6-NaCl
H2 + 00 > C1-C4 Hydrocarbons (2-8)
180°C, 1 atm. (CH3C1)
system was believed to be due to the strong lewis acid solvent. In
this medium bifunctional activation of carbon monoxide could occur
in such a manner that the oxygen end of a bound carbonyl group could
interact with the Lewis acid as shewn in Equation 2-9. These

11
results were confirmed by Coliman et al. and he proposed that the
active catalyst or catalyst precursor in the homogeneous melt system
is IrCl(OO)3.6 The presence of methyl chloride was reported as a
product in the work indicating the consumption of aluminum
M-CSO—>A12C16 (2-9)
chloride during the reaction. The methyl chloride was proposed to
be an intermediate formed during the reaction which was involved in
further homologation and hydrogenation reactions to yield the
observed hydrocarbon products.
Methyl chloride is an important chemical commodity.38 It is
used in the production of organosilioon compounds, in the production
of tetramethyl lead and as a solvent in the production of
methyloellulose. As a solvent methyl chloride has cerne into use in
the last 20 years for the elimination of oils, fats and greases from
surfaces.
The industrial production of methyl chloride is accomplished by
two commercial processes.39 These are the methanol-hydrogen
chloride process and the methane-chlorination process as shown below
in Equations 2-10 and 2-11.
HC1 + CH30H > CH3CI + H20 (2-10)
CH4 + Cl2 > CH3CI + HC1 (2-11)
The production of methyl chloride from methanol is done usually
in the gas phase over activated alumina at 200-300°C.
Monochlorination of methane is done in the liquid phase using KC1

12
and CuCl melts. In the formation of methyl chloride,
polychlorinated methanes are also produced. Selectivities of 98-
99% are obtained for the methanol-HCl process.
An attractive alternative method for the direct production of
methyl chloride would be from carbon monoxide, hydrogen and hydrogen
chloride as shewn in Equation 2-12.
catalyst
H2 + 00 + HCl > CH3CI + H20 (2-12)
Vannice reports the production of methyl chloride frem
synthesis gas and HCl at 270°C and 5 atmospheres pressure on a
catalyst containing supported Group VIII metals on acidic supports
such as alumina.40 Along with methyl chloride, the formation of
multichlorinated methanes, ethane and propane were also reported.
In Table 2-3 is a listing of the possible reactions as well as the
thermodynamic feasibility for the formation of methyl chloride.41
Table 2-3. Possible Reactions and the Thermodynamic Feasibility
(in keal/mol) for the Formation of Methyl Chloride.
CH3OH + HCl > CH3CI + H20 = -7.82 AG400 = "5.98
CH4 + Cl2 > CH3CI + HCl &G298 = -22.89 AG40o = "25.95
2H2 + 00 + HCl > CH3CI + H20 AG^s = -13.85 AG400 = -6.51
Prior work conducted in this laboratory led to the discovery of
a supported phosphine substituted tetrairidium carbonyl cluster
which was shewn to exhibit high activity for the formation of methyl

13
chloride in the presence of H2, 00 and HC1.42 The reaction
proceeded under very mild reaction conditions of 25-100°C and 1
atmosphere pressure as shewn in Equation 2-13.
fo-Si-(CH2) 2-PEh2)xIr4 (°°) 12-x
2H2 + 00 + HC1 > CH3C1 (2-13)
25-100°C, 1 atm.
The coordinated metal carbonyl cluster was prepared by an
initial functionalization of the support. This was accomplished via
a condensation reaction of the surface hydroxyl groups of an
inorganic oxide support such as alumina or silica with the ethoxy
groups of the silane, (OEt) 3SiCH2ai2Pi*12,43 as shewn in Equation 2-14.
-j-QH + (OEt) 3SiCH2CH2PFh2 > (0) x-SiCH2CH2PFhh2 + 3C2H5OH
(2-14)
The number of fo-Si bonds between the support and the silane
linkage is represented as x. The remaining alkoxy groups from the
silane are proposed to be hydrolyzed to yield Si-OH and ethanol.43
The phosphine substituted tetrairidium carbonyl cluster was
assembled from the precursor complex as shewn in Equation 2-15.
ij- (0) x-SiCH2CH2PIh2 + Ir (00) 2C1 (H2N-^-CH3)
Zinc, 00
>
2-methoxyethanol
(0) x-SiCH2CH2PEh2) xlr4 (00) 12_x
(2-15)

14
The synthesis and characterization of these supported clusters by
infrared spectroscopy has been previously reported and shewn to
result in the formation of the mono-phosphine and di-phosphine
substituted clusters.44'45
The catalyst was initially tested in a 3:1 Al2Cl6-NaCl melt
salt under reaction conditions similar to those employed for the
previously reported homogeneous Ir4(00)-^-A^Clg/NaCl system.
Results similar to those previously reported6 were obtained such
that methane, ethane and methyl chloride were detected as products.
The supported phosphine substituted iridium catalyst was shown to
leach the iridium cluster from the support during the reaction
producing the homogeneous Ir4(CO)12-Al2Clg/NaCl system. To
circumvent the problem of catalyst leaching the supported cluster
was tested in the presence of H2, CO and HC1 and in the absence of
Al2Clg/NaCl. In all cases the same activity and selectivity
resulted as previously observed. The activity of this system was
shewn to be dependent upon a number of factors including the degree
of stirring during catalyst preparation, temperature of the reaction
with synthesis gas and HC1 and metal loading.
A later study was conducted to investigate the above effects
with catalyst activity and the cluster stability during reaction.
It was discovered that the previously reported results for the
formation of methyl chloride were clouded by the presence of
adsorbed 2-methoxyethanol which was introduced onto the surface of
the support during preparation of the phosphine supported cluster.46
A number of attempts were investigated to remove adsorbed 2-

15
methoxyethanol which were unsuccessful. Investigation of
alternative routes to synthesize the supported phosphine substituted
tetrairidium cluster resulted in the formation of materials which
did not exhibit the high level of activity and selectivity for the
formation of methyl chloride as the supported iridium cluster
prepared in the presence of 2-methoxyethanol. In these alternative
systems it was proposed that the formation of methyl chloride
resulted from the reduction of carbon monoxide.46 Control
experiments shewed that a contribution to the formation of methyl
chloride was due to impurities in the system introduced during
preparation of the catalyst.
Investigation of the material by infrared spectroscopy after
reaction with H2, 00 and HC1 supported the decomposition of the
catalyst to produce multinuclear complexes and IrCl(C0)3. As the
reaction temperature was increased, it was proposed that the
multinuclear iridium complex was converted to IrCl(GO) 3 or Vaska's
complex on a phosphinated support. It was also preposed that the
stabilized multinuclear complex was active for reduction of carbon
monoxide while IrCl (GO) 3 was inactive. A mechanism was preposed
which accounted for the various routes for the formation of methyl
chloride and other products.46 Figure 2-1 illustrates the proposed
mechanism summarizing the formation of methyl chloride frcrni various
routes. Included in the figure are pathways where by impurities in
the system (such as adsorbed 2-methoxyethanol) may decompose to
methyl chloride as well as a cluster fragmentation pathway believed

A Proposed Mechanism for the Formation
of Methyl Chloride from the Phosphine
Substituted Iridium Clusters,

^-irrh2)mif4ico)y
a» - 200
w"4
NCI
3“
rrafMAUtioii
<
â–  lfh Load
M.M Ir)
dacoapoa 1 tlon
•( ay*toa
iapurltlaa
li-100'C
(-l.lt Irl
raducad
carboo
apaclaa
(yiachar - Tropach Kachanlaa) -a
Cl Cl I Cl, â–  Cl, Cl
.H I Alt
, Carbon Monoxlda
^Induction Hachan!
(Flyura J - 11)
Multlnuclaar
Cpaclaa
(Activa)

18
to yield methyl chloride via reduction of carton monoxide upon
reaction with H2, 00 and HC1.
Results of the previous studies of the supported iridium
carbonyl cluster suggest that stabilization of a multinuclear
iridium carbonyl ccnplex onto an oxide support could result in the
formation of an active system for the catalytic reduction of carbon
monoxide in the presence of hydrogen and hydrogen chloride to
produce methyl chloride. The formation of methyl chloride from
synthesis gas and HCl(g) under mild reaction conditions would be
extremely attractive from an industrial standpoint. For these
reasons, as well as to get a better understanding of the interaction
of iridium carbonyl clusters with oxide supports and Lewis acids
continued investigation of this system is warranted.
B. Experimental
Materials
Iridium carbonyl, IrCl(CO)3, and IrCl3*H20 were purchased from
Strera Chemical Company. Ihe Lew Temperature Shift (LÍES) methanol
catalyst was supplied by United Catalysts. Aluminum chloride,
anhydrous 99.997%, was purchased from Alfa Products. Iron chloride,
anhydrous, and antimony pentachloride were purchased from Aesar.
Aluminum bromide was purchased from Fischer. All metal complexes
were used as purchased unless otherwise stated. Solvents were dried
by distillation over CaH2 or P205 and stored over 4°A molecular
sieves. The 2-methoxyethanol (Kodak, scintillation grade) was used

19
without further purification. The support material was Fisher, acid
Brockman Activity I (80-200 mesh) alumina, or Davison grade no. 62
silica gel purchased frcm W.R. Grace and Co. This alumina was
determined to have a specific area of 180 n^/g.47 The silica gel
had a specific area of 340 n^/g, a pore diameter of 14nm, and a pore
volume of 1.1 cm3/g. When used for direct bonding of the cluster,
all powdered oxides were first heated under vacuum at 350°C for 15
hours to remove water. When used for functionalization the powdered
oxides were dried at 140°C prior to use.
All silanes where purchased frcm Petrarch Systems, Inc., and
vised without further purification.
Hydrogen was purchased frcm Aireo. Carton monoxide (CP grade,
99.5%) and hydrogen chloride (isoelectronic grade, 99.99%) were
purchased frcm Matheson Gas Products. The HC1 feed gas was checked
for chlorocarbons which were not detected. All gases were used
without further purification.
Instrumentation
All air sensitive manipulations were performed in an Aldrich
inert atmosphere glove bag. All syntheses were performed under
either a nitrogen or carbon monoxide atmosphere. Infrared spectra
were obtained as Nujol mulls with a Nicolet model 5DXB spectrometer
using NaCl salt plates. The elemental analyses for iridium were
performed by Galbraith Laboratories, Knoxville, Tennessee. Gas
chromatographic analyses were performed by using a Model 940 FID
Varian chromatograph equipped with a 1/8 in. X 8ft. stainless steel

20
Porapak Q column. The column temperature was maintained at 130°C.
Gas chromatographic mass spectrometry were performed by Dr. Roy King
of the Microanalytical laboratory, University of Florida,
Gainesville, Florida. Samples were run by using a AEI MS 30 mass
spectrometer equipped with a KDITQS DS55 data station. The system
was equipped with a PYE Unicam 104 gas chromatograph containing a
1/4 in. X 5ft. Porapak Q column. The system was equipped with a
dual magnesium anode X-ray source and a double pass cylindrical
mirror electron analyzer. Data acquisition was controlled by a
Digital PDP computer. All ESCA data were obtained through the
courtesy of Dr. Tern Gentle, Dow Coming Corporation, Midland,
Michigan. The samples were run in a Perkin-Elmer Model 551
stainless steel ultra-high vacuum chamber equipped with a dual
magnesium x-ray source and a double pass cylindrical mirror electron
analyzer. Data acquisition was controlled by a Digital PDP
computer.
Fixed Bed Flew Reactor
A glass flow system as shown in Figure 2-2 was used to test the
catalytic activity of the supported iridium complexes for
hydrogenation of carbon monoxide in the presence of HCl(g). This
system is similar to that previously described by Weiss.46 The
gases were allowed to enter the system and mix via a three stage
bubbler with teflon needle valves to control the individual gas flow
rates. The 00 and H2 gases were bubbled through mineral oil while
the HCl gas was bubbled through sulfuric acid. The catalyst was

Figure 2-2. A Diagram of the Fixed Bed Flew Reactor.


23
placed in a glass tube with a glass frit to hold it in place and the
gases were allowed to flew over the catalyst. Temperatures were
regulated by using a model 123-8 Lindberg thermostated tube furnace.
Sample ports before and after the catalyst allowed for analysis of
the gases. The gases were collected by using a pressure-lok 2ml
syringe purchased from Precision Sampling Corp. and analyzed by GC.
The addition of a glass spiral trap to the system allowed for
trapping of the gases in a dry ice/acetone slush.
Preparation of a Phosrhinated Support
The phosphinated supports were prepared by a procedure similar
to those previously reported in the literature.33'48 Under a
nitrogen atmosphere 5.0 g of dried support such as alumina or silica
gel was added to a stirred solution of 150ml of toluene or benzene.
The mixture was heated to reflux and 0.45ml (1.25X10-3 moles) of 2-
(diphenylphosphino) ethyltriethoxysilane was added by syringe. This
reaction was allowed to continue for 12-15 hours. The
functionalized support was collected by vacuum filtration followed
by successive washing with the toluene or benzene solvent. The
functional ized supports were dried under vacuum at room temperature
for 24 hours prior to use. For the phosphinated supports the
loading of accessible phosphine substituents was 1.25 X 10“3 moles
per gram of support. An analogous synthetic procedure was employed
for functionalization of the supports with 2-
(diphenylphosphino) prcpyltrimethoxysilane. The phosphinated
supports are represented as (S)-FEh2 where S= A1203 and Si02.

24
Preparation of the Supported Triphosphine Substituted Iridium
Carbonyl Clusters
The phosphine substituted iridium carbonyl cluster was prepared
by a procedure similar to that reported by Karel and Norton.49 A
total of 1.3g Ir4 (00) 12 was added to a stirred solution of toluene
or benzene solution containing 5.0g phosphinated support (1.25X10-3
moles of phosphine). The reaction was allowed to proceed at reflux
temperature for 24 hours. The brcwn-yellcw resin was collected by
vacuum filtration and dried voider vacuum at room temperature for 24
hours. The characterization of this material by infrared
spectroscopy has been previously discussed.46 This material is
represented as (S)-(PFh2)xIr4 (00) 12_x where x=l,2 or 3.
Preparation of Directly Deposited Tetra iridium Carbonyl Clusters on
the Support
The method used to support lr4(00) 12 was to adsorb the carbonyl
cluster from solution onto an inorganic oxide support such as
alumina or silica gel. A total of 0.5g lr4(00)12 was added to a
stirred or benzene solution of 5.Og support. The reaction was
allowed to proceed at reflux temperature for 15 hours. The yellow
resin was collected by vacuum filtration and washed with solvent
benzene. The cluster deposited supports were dried under vacuum for
24 hours prior to use. The characterization of these materials by
infrared spectroscopy is discussed in the results section. This
material is represented as S/Ir4 (00) 12 where S= Al203 and Si02.

25
Preparation of the Aluminum Chloride Tetra iridium Carbonyl Cluster
Treated Supports
A total of 0.33g A12C16 was added to a stirred carbon
tetrachloride solution containing l.Og of tetrairidium carbonyl
cluster on alumina or silica gel which had been deposited on the
support as previously described. The reaction was allowed to
proceed for 12 hours at 50°C. The Lewis acid treated materials were
collected by vacuum filtration and washed with carbon tetrachloride
solvent. The materials were dried under vacuum at room temperature
for 24 hours prior to use.
Another procedure was also employed to prepare the supported
aluminum chloride tetrairidium carbonyl complexes. This reaction
was conducted under a nitrogen atmosphere. A total of 0.5g A12C16
was added to a stirred solution of l.Og support in carbon
tetrachloride solvent. The reaction was allowed to proceed for 12
hours at 50°C. The aluminum chloride treated support was then
collected by vacuum filtration, washed with carbon tetrachloride
solvent and dried under vacuum for 12 hours. The aluminum chloride
treated supports were then reacted with tetrairidium carbonyl
clusters where a total of O.lg lr4(00)12 was added to a stirred
solution of l.Og aluminum chloride treated support in carbon
tetrachloride solvent. The reaction was allowed to proceed for 12
hours under nitrogen. The solids were collected by vacuum
filtration and dried under vacuum at room temperature for 24 hours
prior to use. The Lewis acid treated deposited materials are
represented as S/Ir4 (00) 12/A12C16. The characterization of these
materials is discussed in the results section.

26
Preparation of Other Lewis Acid Treated Deposited Tetrairidium
Carbonvl Clusters
All other lewis acids such as SbCls, FeCl3 and AlBr3 were
reacted with the deposited tetrairidium carbonyl cluster in an
analogous procedure enployed for the reaction with aluminum
chloride. Appropriate amounts of the Lewis acid were added to a
stirred solution of deposited 1x4 (00) ^ The reactions were allowed
to proceed for 12 hours and the solids were collected by vacuum
filtration then dried under vacuum at room temperature for 24 hours
prior to use.
Preparation of Aluminum Chloride Treated Commercial Methanol
Catalysts
The A12C16 treated commercial methanol catalysts were prepared
by using an analogous procedure enployed for reaction of deposited
iridium carbonyl with aluminum chloride. The catalyst enployed had
the composition CuO/ZnO/Al203 (42:47:10). A total of 2.0g of United
Catalysts Lew Temperature Shift (LIS) Catalyst was added to a
stirred mixture of 0.66g aluminum chloride in 50ml of 0C14. The
reaction was allowed to proceed for "15 hours under nitrogen. The
solid resin was collected by filtration, washed with carbon
tetrachloride solvent and dried under vacuum at room temperature for
24 hours prior to use.

27
Reaction of the Supports and the Supported Metal Complexes with
Carton Monoxide. Hydrogen and HClfq)
A total of l.Og of solid material was placed into the glass
fritted reactor tube. The reactor tube was placed into the fixed
bed flow reactor system previously described in Figure 2-2. A
typical reaction was run at 125°C with the individual H2:00:HC1 gas
flews at a ratio of 2:1:0.5 combining to give an overall flew rate
of 2ml/30-60 seconds. The reactant and product gases were monitored
by gas chromatography. Investigation of the active species for
carbon monoxide reduction by infrared spectroscopy is discussed in
the results section.
C. Results and Discussion
Re investigation of Earlier Work of the Supported Fhosphine
Substituted Tetra iridium Carbonyl Cluster
The supported phosphine substituted tetrairidium clusters were
prepared as described by Weiss.46 An inorganic oxide such as
alumina or silica gel was functionalized via a simple condensation
reaction of the alkoxy groups of silane and the hydroxyl groups of
the surface of the support as shown in Equation 2-16. Then the
tetrairidium carbonyl cluster was reacted with the phosphino groups
of the functionalized support as shewn in Equation 2-17. These
materials were characterized by infrared spectroscopy and shown to
contain mostly the tri-phosphine substituted cluster as well as some
mono-phosphine and di-phosphine substituted tetrairidium carbonyl

28
clusters as previously described.46 The majorVco bands for the
supported phosphine substituted iridium clusters are listed in
Table 2-4.
(OEt)3SiCH2aí2PFh2 J
q-OH > ^-0-Siai2CH2PFh2
(2-16)
Ir4 (CD) 12
^-o-!
SiCH2CH2PFh2) xlr4 (00) 12_x (2-17)
Hie supported phosphine substituted clusters were investigated
for catalytic activity in the presence of 00, H2 and HCl(g) at 75°C
in the fixed bed flew reactor previously described in Figure 2-2.
Results similar to those previously reported46 were observed upon
reaction of the phosphine substituted cluster with the reactant
gases as detected by chromatography using a Porapak Q column at
130°C. Hie major product observed in these systems is ethyl
chloride which was previously unreported. Other products observed
by chromatography include methane, methyl chloride, ethane and
acetaldehyde. Water and carbon dioxide were also confirmed by
GC/MS. It was found that if the amount of HCl(g) present in the
system was reduced, the identification of ethanol by gas
chromatography was possible.
As described earlier, when the supported phosphine substituted
tetrairidium carbonyl cluster was prepared in the presence of 2-
methoxyethanol solvent from the reaction of the functionalized
support with the iridium precursor complex lrCl(C0)2 p-toluidine,
methyl chloride was found to be the major product detected upon
reaction of the supported cluster with the gases.42 An in depth

29
Table 2-4. Major V (oo) Bands in the Infrared Spectra for
Fhosphine Substituted Ir4 (OO) 12 and Ir^CO)^.
Compound
v (Sft
Ref.
Mixture of
j, 2lr4 (00) 11( 10a
2083 (w), 2070(w), 2053(s)
2030(S), 2020(S), 2000(s)
1845(w), 1825 (m), 1795 (w)
42,46
Al203-(PEh2)3Ir4(C0)9b
2045(S), 1995(vs), 1791 (m)
1774 (w)
46
Ir4 (00) 22
2073(sh), 2059(s), 2020 (m)
2000 (w)
c
Ir4(C0)12
2075(w), 2058(S), 2020(m)
2003(VW), 1994 (W)
Al203/Ir4(00)12
2075(w), 2062(S), 2022 (m)
1996(W)
Si02/Ir4(CD)12
2075sh), 2063(s), 2023(m)
1996(w)
Al203/Ir4(C0)12/Al2Cl6
2127(W), 2105(mw), 2062(s)
2022(m), 1996(w)
Si02/Ir4(00)12/Al2Cl6
2111(W), 2075(Sh), 2063(s)
2041(W), 2023(m), 1996 (W)
Al203/IrCl(CO)3
2082(s)
Al203/IrCl (°°)3/Al2Cl6
2071(S)
a= cluster formed by reduction of IrCl(00)2(p toludine)
b= cluster formed by substitution of carbonyl ligands in Ir4(CO)12
c= Crawford, et. al. J. Catal.. (1983), 83, 454.
* s=strong, m=moderate, w=weak, sh=shoulder

30
investigation of that system revealed that the methyl chloride
product resulted from cracking of residual 2-methoxyethanol adsorbed
onto the surface of the oxide support during preparation of
phosphine substituted cluster.46 A series of control reactions were
conducted on the system containing the supported phosphine
substituted iridium cluster50 prepared from reaction of the
phosphino groups of the functionalized support with the carbonyl
groups of the tetrairidium carbonyl cluster as shewn in Equations 2-
16 and 2-17. These experiments were conducted in order to determine
if carbon monoxide was being reduced catalytically.
A series of control reactions were conducted on the system
containing the supported phosphine substituted iridium cluster50
prepared from reaction of the phosphino groups of the functionalized
support with the carbonyl groups of the tetrairidium carbonyl
cluster as shown in Equations 2-16 and 2-17. These experiments were
conducted in order to determine if carbon monoxide was being reduced
catalytically. The necessity for investigation of all the possible
routes for the formation of methyl chloride is obvious in view of
the activity of the previously described activity reported by
Miller.42 The production of methyl chloride in these systems could
result from adventitious carbon sources introduced into the system
during preparation of the catalyst. The reactions conditions
employed are those expected to lead to reduction of 00 in a
catalytic system.
The results of these experiments are found in Table 2-5.
Contained in Table 2-5 for comparison are the previously described

Table 2-5.
SUPPORT
1 Al -PPhjIrntCO),,
and
A1 (-PPh^jIr^CO)
2 A1 -PPh2
or
SC -PPh2
3 A1203 or
sio2
Control Reactions for the Fhosphine Substituted
Supported System.
MOLES PROD.
SEC"1 CRAM
PREPARATION PRYING PROCEDURE CAS FLOW PRODUCTS CATALYST"1
2-methoxyethanol uider AO pal
vacuus
AO
•C, 12 hrs.
h2/co/hci
CH^CH^Cl
-uf12
CO at 90 »C from Ir(CO)2 -
CH3C1 at
75
•c
-10-10
Cl • p-toluldlne
stirred with 2-aethoxyethanol
s
o
c
i
AO
•C. 12 hrs.
h2/co/hci
CH3C1 at
75
•c
-10'10
uider AO pal CO at 90 *C
vacuus
80
•C, 12 hra.
h2/co/hci
CH3C1 at
75
•c
-lO’10
2~nethoxyethanol under ACX pal
s
o
c
fi
AO
•C, 8 hra.
h2/co/hci
ch3ci
-lO*10
CO at 90 *C
at 60 »C

Table 2-5 Continued
SUPPORT
4 A1
5 A1
6 A1
Note:
PPh2
PPh2
-PPh2
MOLES PROD.
SEC’1 cram
PREPARATION
DRYING PROCEDURE GAS FLOW
PRODUCTS
CATALYST"1
reflux in toluene using
vicuui AO »C. 12 hra. H2/C0
CHjOH at 60
•C
-10" n
(OCH3)3S»-C3H6PPh2
H^CO/HCl
CH3C1 at 60
•c
-10"11
reflux in toluene using
vacuum 80 *C, 12 hrs. Hj/CO
CH^CH?0H at
o
•
o
vO
1
o
1
O
1
O
1
(OCH2CH3)3Sl-C2H„PPh2
H2/C0/HC1
CHjCHjCl at
60 *C
t
o
1
o
•
o
1
Ci^CHjCl.
1
o
1
o
1
°l_
CH^Cl at 100 »C
1
o
1
o
1
o
1
h2/hci
CH^CH^l v
1
o
•
o
1
o
1
ch3ci
1
o
1
•
o
•
N
T > 100 *C
reflux in benzene using
vacuua 80 *C. 12 hra. H2/C0
CH3CH2OH at
60 *C
o
1
o
1
(OCH2CH3)3-SlC2K,PPh2
H2/C0/HC1
CH3CH2C1
1
o
1
o
1
o
1
at 100 »C
h2/hci
ch3ch2ci.
1
o
1
o
1
o
1
CH3C1 at
-10*13
T > 150 *C
u>
to
In 1 and 2, A1 -PPh2 was first prepared iron reaction of A12C>3 with (OCH^Hj)jSl-C2H|,PPh2 refluxing benzene.
SC -PPh2 was prepared In a similar manner using S102.
In 1, 0.31% iridium loading.

33
results from cracking of 2 -methoxyethanol solvent over the inorganic
oxide support. The results of the control experiments involving the
cracking of 2-methoxyethanol by HC1 to produce methyl chloride are
shewn in experiments 1-3. As shewn in the Table, ~10“10 mol CH3CI/
sec/g material was observed even in absence of the iridium cluster.
As previously described the amount of observed CH3CI in these
systems was dependent upon a number of factors including the degree
of stirring during preparation, loading of the phosphino silane, and
the amount of HC1 present in the reactant gas. The results of these
control experiments indicate that the formation of methyl chloride
is a result of the cracking of 2-methoxyethanol solvent used to
prepare the supported phosphine substituted cluster.
In Table 2-5, experiments 4 and 5 were conducted in an attempt
to investigate the possibility that alkoxy groups from the
functionalizing agent could lead to the formation of alkyl chloride.
Alumina was functionalized with (CH3O) 3SiC3HgP(CgH5) 2 and
(C2H50) 3SiC2H4P(C6H5) 2 in toluene and benzene solvent (experiments
4-6). In both instances the alcohol corresponding to the alkoxy
group was detected when H2 and 00 were passed over the
functionalized support at 60°C. The alkyl chloride was observed
when the gas mixture of H^/OO/HCl was passed over the same support.
These observations are interesting in view of the reaction reported
by Waddell et al.43 and by Studer and Schrader.44 In these
articles, the alkoxy groups in (alkoxy) 3Si(CH2)xPFh2 are reported to
be hydrolyzed off of the silicon in the course of functionalization
producing the alcohol and forming hydroxyl groups bound to the

34
Cp H—C—H
H—C —
I
—Si-
0
•H
•OvCH2CH3
%
\
''HO
H H
I I
O-C-C-H OH
I I
H H
7/////////////////////7T777
Figure 2-3. Structure of the Ethoxy Surface Species Formed
During Functionalization of the Alumina Oxide

35
inorganic oxide. If this hydrolysis occurs, the alumina surface
retains the alcohol or alkoxy groups as shewn in Figure 2-3. The
alcohol products corresponding to the alkoxy groups from the silane
are obtained upon reaction with H2 and 00 and upon addition of HC1
to the reactant gases the corresponding alkyl halides are formed
(experiments 4-6).
When a gas mixture of H2/OO/HCI was passed over the support
functionalized with (C2H50)3SiC2H5P(C5H5)2 in toluene (experiment 5)
at 100°C, methyl chloride was observed. This product was not
detected when benzene was used instead of toluene as a solvent
during the functionalization procedure. The formation of methyl
chloride in addition to ethyl chloride was detected in the benzene
preparation when H2 and HC1 were passed over the solid at
temperatures greater than 150°C. Although at temperatures of 100°C
the formation of methyl chloride is detected from the toluene
preparation (experiment 5), the same preparation in benzene
(experiment 6) did not result in the detection of methyl chloride at
this temperature. In the benzene preparation, methyl chloride
production was observed only at temperatures above 150°C. It is
possible that the methyl chloride is produced from the cracking of
toluene in experiment 5. The detection of CH3CI above 150°C in
experiment 5 is believed to occur fran decomposition of the ethoxy
groups present on the phosphino silane, or on the alumina surface
and cracking of benzene does not appear to occur.
As discussed previously46 the cracking of toluene to produce
methane (and benzene) is thermodynamically possible. This type of

36
reaction could result in the formation of methyl fragments on the
surface of the support which then react with HCl(g) present to
produce methyl chloride. As shown in Table 2-4, the quantity of
methyl chloride formed in the experiments conducted in the absence
of 2-methoxyethanol is lew.
A reaction scheme corresponding to the decomposition of the
ethoxy groups from the phosphinosilane to form CH3C1 is represented
in Figure 2-4. In this scheme, reaction of the adsorbed ethoxy
groups would lead to ethanol production. Dehydration of coordinated
ethanol or ethoxy groups would result in the formation of ethylene
while dehydrogenation of ethanol produces acetaldehyde.
Acetaldehyde is detected in the early phases of the experiments by
GC and GC/MS. Ethylene/ethane is detected throughout the experiment
as a minor byproduct. As shewn in Figure 2-4, ethylene may then
react with HC1 to produce ethyl chloride which is the major product
fran the reaction of ethanol or ethoxy groups with HC1. Ethylene
may be exacted over the alumina surface producing carbon species.
Reaction of the carbon species with hydrogen and HC1 would account
for the methane and methyl chloride observed in the experiments with
the ethoxy silane. All of these reactions are further complicated
by reactions involving the intermediate species. Evidence for such
a scheme is supported by reports in the literature. Several reports
indicate that ethanol can be converted over inorganic oxides to
ethylene,51-53 ethane,51 and acetaldehyde54'55 all of which were
observed as minor products in the reactions. It is generally
recognized that olefins are an important source of carbon formation

37
HO OCH,CH
2'"’1 *3
CH.CHO
â– H? 7
T>I50°C / \ + CH3CH2OH — H“o CH2=CH2
7777777 77777
ch2=ch2-
ch3ch2ci
CARBON SPECIES
h2, hci
H2^\
ch4
CH3CI
Figure 2-4. Schematic Representation of the Decomposition
of the Ethoxy Groups at Elevated Temperatures

38
involved in catalytic cracking.56 Reports indicate that over a
metal surface ethylene may decompose to carbon atoms via an
acetylene intermediate.57'58 It is proposed that similar chemistry
is occurring whereby decomposition of ethoxy groups eventually lead
to the formation of methyl chloride.
In order to determine if the methyl chloride or other products
detected are being produced from the catalytic reduction of carbon
monoxide with H2 and HC1 it is necessary to remove the organic
residues from the surface of the supported iridium clusters. An
initial method of investigation in this work involved passing a
gaseous mixture of H2 and HCl over the phosphine functionalized
support at 150°C until ethyl chloride or other products were no
longer detected in the exit gas. Reaction of the HCl treated
material with Ir4(GO)12 in refluxing resulted in supporting the
intact cluster. Upon passing a gaseous mixture of H2, CO and HCl
over the supported cluster at 70°C, no products corresponding to
those expected from the reduction of carbon monoxide or from organic
residues introduced during synthesis were detected.
These results of the reinvestigation of the earlier work42'46
on the phosphine supported iridium cluster indicate that any
reduction of CO by the system is masked by the presence of organic
residues adsorbed onto the surface of the oxide support. These
residues were shewn to be introduced into the system during
preparation of the material. The support functionalization
procedure was shewn to cause the most misleading results in the
previously reported study. It was shown that through a series of

39
control experiments50 (see Table 2-5) that the decomposition of the
alkoxy groups present on the phosphinosilane linking agent led to
the formation of significant amounts of halogenated products.
Attempts to remove these residues by treating the supports with H2
and HCl(g) resulted in the formation of inactive materials for
reduction of carbon monoxide.
Another approach was undertaken to support the iridium cluster.
The objective of this study was to prepare the supported iridium
carbonyl cluster in the absence of any organic residues as well as
to optimize conditions for the bifunctional activation of carbon
monoxide. The main approach was to prepare a heterogeneous analog
to the reported Ir4 (00) j^/A^Cls-NaCl system previously reported by
Muetterties et al.5 and Coliman et al.6 This was originally the
goal of the previously described systems however the difficulties
encountered (which were described above) caused the original
objective to be unattainable.
Investigation of Directly Deposited Ir^(00)12
In order to eliminate adventitious carbon sources in the
system, lr4(00)12 was directly deposited onto an inorganic oxide
support such as alumina or silica gel. First the oxide support was
heated under vacuum at 300°C to remove any water or organic residues
which may be present and then the tetrairidium carbonyl cluster was
adsorbed from benzene solution onto the surface of the oxide support
as shewn in Equations 2-18 and 2-19.

40
-h2°
Al2*^3 > Al2°3 (2-18)
AI2O3 + Ir4(O0)12 > Al2O3/Ir4(O0)12 (2-19)
The directly deposited iridium cluster was characterized by
infrared spectroscopy. The infrared spectrum of lr4(00) 12 adsorbed
caito alumina is shewn in Figure 2-5A and the major V oo bar*!3 ate
listed in Table 2-4. A similar infrared spectrum was obtained for
reaction of Ir4 (00) 12 with silica gel (see Figure 2-6A). The four
band pattern present in Figures 2-5A and 2-6A are indicative of
iridium carbonyl both in the solid state and in solution. It is
proposed that aggregates of Ir4 (00) 12 exist on the support. The
broad absorptions in the 2100-2200 cm"! region probably involve
molecules on the surface of the aggregate interacting with acid
sites on the support.
Assignments of the metal carbonyl stretching modes for
Ir4 (00) 12 have been reported by Abel and ocworkers.59 As noted
previously,60 the spectrum of lr4(00)12 in the solid state closely
resembles supported Ir4(00)12 although improved resolution in this
and previous work has revealed some differences in the relative
intensities of the bands compared to those previously reported by
Abel.59 The 2062 and 2022 cm-1 bands of Ir4(00)12 in the solid
state and on alumina and silica supports are assigned to the two T2
infrared-active carbonyl stretching modes. Abel attributed the 1995
cm-1 band to the mode which is infrared inactive in exact
symmetry, but which becomes active on a slight distortion towards

% TRANSMISSION
41
a = I 996 cm'
b = 2022 cm'
c = 2062 cm"
d = 2075 cm"
e = 2105 cm"
f =2127 cm"
Figure 2-5. Infrared Spectra of Ir4 (00) 12 Deposited onto Alumina
(A) Before and (B) After Treatment with A12C16.

Vo TRANSMISSION
42
Figure 2-6. Infrared Spectra of Ir4 (C30) ^2 Deposited onto Silica
Gel (A) Before and (B) After Treatment with A12C1&

43
E>2ci symmetry. This band is observed in the solid but not in
solution.59 We observe the 1995 cm-1 band and also observe one at
2075 cm-1 for lr4(00)12 on alumina and silica. The appearance of
the 2075 can-1 band observed in our complexes could be due to further
splitting of the T2 mode (which contains the E mode of the M(00) 3
unit) by distortion toward lower symmetry.
The spectra of iridium carbonyl deposited onto alumina and
silica gel exhibit strong 2062 and 2022 cm-1 absorbances
respectively indicating that most of the material present on the
support is lr4 (CD) 12.
Investigation of Supported Ir^(00)for Catalytic Activity Upon
Reaction With H2. CP and HCl(g)
The deposited iridium carbonyl clusters were investigated for
catalytic activity for reaction with H2, 00 and HCl(g) using the
fixed bed flew reactor previously described and shewn in Figure 2-2.
Upon passing a gaseous mixture of H2, 00 and HC1 over the supported
Ir4 (00) 12 cluster the formation of methane, ethane, methyl chloride,
acetaldehyde, ethyl chloride and minor amounts of dichloromethane
were detected by using gas chromatography as shewn in Figure 2-7.
GC/MS of the product gas stream also confirmed the formation of
carbon dioxide and water. The major product formed in this system
is methyl chloride. The activity of the Al203/Ir4 (00) 12 system for
the formation of methyl chloride is between 10”11 to 10”12 mol
CH3Cl/g/sec. A plot of the formation of methyl chloride versus time
is shewn in Figure 2-8. The observed activity of the system is
similar to that previously reported for the phosphine

44
a= methane
Figure 2-7. A Sample Gas Chrcmatograph of the Products Formed
Upon Reaction of H2, GO and HCl(g) over the Supported
Iridium Clusters at 125°C and 1 Atmosphere.

45
TIME (HOURS)
Figure 2-8. Activity Curves for the Various Supported
Iridium Carbonyl Clusters for the
Formation of Methyl Chloride.
(A) Al2O3/Ir4(C0)12/Al2Cl6
(B) Si02/Ir4 (00) 12/A12C16 (C) Al2O3/Ir4(C0)12

46
substituted supported iridium carbonyl clusters prepared with the
ethoxy silanes.44 In the previously reported system organic
residues present on the support were shewn to contribute to the
CH3CI formed.
In the directly deposited system the absence of these organic
residues confirms the reduction of carbon monoxide either from the
reactant gas or fran the carbonyl grot?» directly bound to the
original cluster. While a complete mass balance was not conducted
the total moles of detected product in this system is significantly
less than the number of moles of CD from the original supported
cluster. These results suggest that the observed products are
primarily from deccnposition of the cluster.
Adsorbed metal carbonyl clusters will react with the surface
hydroxyl groups present on inorganic oxide supports.60'61 This type
of interaction has been reported to occur for adsorbed iridium
carbonyl on alumina supports. Iridium carbonyl, lr4(00)12, may
undergo a decarbonylation reaction with surface hydroxyl groups at
temperatures above lOO'-Hl60 as shewn in Equation 2-20. The carbon
lr4(00)12 + XSOH > Ir4(00)12_x(S0H)x + xCO (2-20)
monoxide evolved is then proposed to undergo reduction in the
presence of H2 and HC1 to produce the observed products.
The thermal decomposition of supported iridium carbonyl on
inorganic oxides such as alumina or silica has been previously
investigated.62-64 Studies in flowing H2 of lr4(00)12 on Al203

47
resulted in the evolution of 00 and CH4 as well as small amounts of
C2H4, C2Hg and 002. It was reported that lr4(00)12 does not lose
its 00 groups until 125°C. The initial decomposition of the metal
carbonyl cluster was believed to occur through both the interaction
of the cluster with the surface hydroxyl groups of the support as
well as direct hydrogenation of the carbonyl ligands. There have
not been any reports of the stability of metal carbonyl clusters in
the presence of H2, CD and HCl. In order to get a better
understanding of the stability of Ir4(CD) 12 under reaction
conditions an infrared study was conducted. These results are
discussed in a later section.
Investigation of the Aluminum Chloride Treated Deposited Iridium
Carbonyl Clusters
The aluminum chloride treated lr4(00)^2 cluster materials were
prepared by reaction of the oxide deposited cluster with aluminum
chloride as shown in Equation 2-21.
Al203/Ir4 (00) u + A12C16 —> M20yir4(00)12/Al2Cl6 (2-21)
The hydroxyl groups of a support have been shewn to react with
Al2Clg according to the following scheme as shewn below in Equation
2-22.65 This reaction could minimize decarbonylation of Ir4(C0)12
through reaction with surface hydroxyl groups and reduce the
possibility of the reaction in Equation 2-20 occurring with the
Al2Clg treated solids. Further attempts to minimize the occurrence
of a decarbonylation reaction was provided by a second sample

48
preparation method. In this case, the support materials were first
reacted with A12C16 followed by reaction with Ir4 (00) 12 • This
- S-O-H
\
2 0 +
/
- S-O-H
ai2ci6
\
-> 2 0
/
"'s\
CH
+ 2HC1
0-A1C1'
(2-22)
method of preparation should minimize the presence of any remaining
hydroxy groups which were not converted to A1C12 groups and prevent
decarbonylation by reaction of hydroxyl groups on the support
surface with carbonyl groups of Ir4 (00) 12 during the A12C16
treatment used earlier.
The aluminum chloride treatment could (i) increase the
stability of the cluster by minimizing cluster interactions with
surface hydroxyl groups upon conversión of the hydroxyl groups to
aluminum chloro groups; (ii) lead to bifunctional activation of
carbon monoxide by forming a Lewis acid adduct with a bound carbonyl
group of the iridium cluster as shewn belcw. The overall result
Ir-C3D —> A1C13
of this treatment should produce a material which exhibits greater
stability and activity for the reduction of carbon monoxide. The
results of reaction of these materials with H2, CD and HC1 are found
in a later section.
These materials were investigated by infrared spectroscopy.
The infrared spectrum of iridium carbonyl deposited onto alumina and

49
silica and then treated with aluminum chloride are shewn in Figures
2-5B and 2-6B respectively. The major V (qo) bands in the infrared
are listed in Table 2-4. The infrared spectrum of the silica
supported cluster is essentially unchanged by reaction with A12C16
except for the appearance of very weak peaks at 2111 and 2041 cm-1.
More pronounced changes occur in the infrared spectrum when
Ir4 (00) i2 supported on A12C>3 reacts with A12C16 as shewn in Figure
2-5B. The spectrum has a high frequency peak of weak intensity at
2127 an-1 and one of moderate intensity at 2105 cm-1. These peaks
have replaced the broad absorption in Figure 2-5A. They are
attributed to the surface molecules of the Ir4 (00) 12 aggregate
undergoing discrete interaction with bound A1C12 species instead of
a variety of surface acid sites. The infrared spectra of the
aluminum chloride treated supports that were subsequently reacted
with Ir4 (00) i2 did not show any differences in region from the
materials in which the support was first reacted with lr4(00)12
followed by reaction with Al2Cl6. The 2105 cm-1 peak in the A1203
supported material is presumed due to a discrete species formed by
reaction of seme Ir4 (00) 12 surface molecules with A1C12. These high
frequency peaks are not seen for Ir4 (00) ^ in solution or the solid
state. These findings indicate chemical reactivity of at least some
of the iridium carbonyl clusters when treated with Al2Cl6.
Interaction of the A1C12 group shewn in equation 2-22 with
metal carbonyls would lead to shifts in the infrared.66 Possible
acid-base interactions include: (1) interaction of the oxygen of a
carbonyl group with the Lewis acid resulting in a decrease in V co

50
of that group and a smaller increase in V co °f t*16 remaining
uncoordinated (terminal) carbonyls of the cluster or (2) direct
interaction between a metal atan and the Lewis acid resulting in an
increase in the V ^ for all carbonyl ligands. The interaction of
the oxygen of a carbonyl group with the lewis acid has been shown to
result in terminal-to-bridging CD shifts as reported by Shriver and
coworkers for Ru3 (CD) 12 interacting with AlBr367 as shewn in
Equation 2-23.
ACID >
§
(2-23)
A third possibility for an increased carbonyl frequency would
involve oxidation of the iridium cluster.
Correa et al.68 has demonstrated that the Lewis acid sites of
alumina can promote 00 insertion. Upon impregnating alumina with
Mn(CD)5(CH3) the presence of an acetyl species with a cyclic
structure as shewn in Equation 2-24 was detected by infrared
spectroscopy.
AI2O3
Mn(00)5(CH3) >
rapid 25°C
CH3
a (OC)Mn—Crr.O
I ;l
Al 0 Al
(2-24)
The A1C12 molecules in contact with the surface of an Ir4 (CO) 12
aggregate probably give rise to the 2105 cm-1 peak for
Al203/Ir4(00)12 (see Figure 2-5B) and the 2041 and 2111 cm-1 peaks

51
for Si02/Ir4 (GO) Y2 (s®6 Figure 2-6B). These peaks could be the high
frequency component of an lr4(00) 12 cluster coordinated to A12C16
coordinating to a metal center or a carbonyl group with the low
frequency ccnponent being too weak to be detected. Oxidation of an
iridium center in sane of the surface clusters to a higher oxidation
state can also cause the frequency of coordinated CD to increase.
Psaro et al.69 reported a 30-40 can-1 increase in the
frequencies of the infrared bands for [0s3(00)n]2- ionicly bound to
the surface of MgO. They preposed that the increase in the carbonyl
frequencies was caused by the interaction of the cluster with a
lewis acid center, probably a magnesium ion surface species. A
similar kind of specific bonding was reported for iron carbonyls
interacting with a proton or with carbocations.67 The fact that the
principle bands at 2062 and 2022 an-1 do not shift for
Ir4 (00) 12/si°2, Ir4 (00) 12/AÍ2°3 or ^ Al2cl6 treated analogues
suggests that most of the material exists as aggregated clusters on
the surface of the support. A summary of all the infrared
absorbances in the carbonyl region for the iridium complexes is
found in Table 2-4.
Investigation of the Aluminum Chloride Treated Supported Iridium
Carbonyl Clusters for Catalytic Activity Upon Reaction with H2, 00
and HClfa)
The aluminum chloride treated deposited Ir4 (00) 12 clusters were
investigated for catalytic activity upon reaction with H2, 00 and
HCl(g) using the fixed bed flew reactor previously described and
shown in Figure 2-2. These materials are proposed to represent the

52
heterogeneous analog of the previously reported Ir4(00)12-A12C16
homogeneous system.5»6
Upen reaction of the supported Ir^OOJ^-A^Clg materials with
H2, CO and HC1 at 125°C high selectivity for the formation of
methyl chloride was observed. The formation of methane, trace C2
products and dichlorcmethane was also detected by gas chromatography
similar to that shown for the Al203/Ir4 (00) 12 system in Figure 2-7.
Carbon dioxide and water were also detected by GC/MS. A comparison
of the activity for the different supported iridium materials is
shewn in Figure 2-8.
The Lewis acid treated materials exhibit reactivity of
approximately two orders of magnitude greater than the deposited
clusters which were not treated. In the deposited iridium carbonyl
clusters which were not treated with aluminum chloride the
reactivity of those material is proposed to represent primarily a
stoichicmetric decomposition of the cluster to the observed
products. This activity is believed to be initiated by interaction
of the carbonyl groups of the original cluster with the surface
hydroxyl groups of the support as previously described60 and shown
in Equation 2-20. The Lewis acid treated solids described here also
exhibit approximately two orders of magnitude greater reactivity
than the previously reported phosphine substituted supported iridium
clusters.46 In those systems it was shewn that organic residues
present on the surface of the oxide support made a contribution to
the observed products.

53
With time the activity of the supported Ir4 (00) 12 materials
decreases and eventually reduction of carbon monoxide is no longer
observed to occur as indicated by the absence of products detected
by gas chromatography. These resulting inactive materials were
investigated by infrared spectroscopy in an attempt to determine the
nature of the iridium species formed. A discussion of these results
is found in a later section.
Comparison with the Homogeneous Ir^ (CD) 12~A12C16 Svsterc
In the previously reported homogeneous Ir4 (CO) ^-A^Clg system
the major product observed upon reaction with H2 and 00 was
ethane.5'6 No oxygenated products were detected in the homogeneous
iridium system unlike typical homogeneous 00 hydrogenation systems
employing metal carbonyl clusters as catalysts. Other products
detected in that system include methane, methyl chloride and
propane. Coliman et al.6 proposed that the methyl chloride produced
was an intermediate species in the molten system which undergoes
further homologation and hydrogenation reactions leading to the
formation of higher hydrocarbon products. However, in the supported
iridium carbonyl system investigated in this study methyl chloride
was observed to be the major product in the reaction of the
supported iridium clusters with H2, 00 and HC1. This increase in
product selectivity may result from two factors. One would involve
the HC1 present in the reactant gases which would convert C-^
intermediates to methyl chloride. The short contact time between

54
CH3C1 and Al2Clg would also minimize subsequent reaction of CH3C1
leading to homologation.6
The catalytic synthesis of hydrocarbons fren H2 and CD over
supported iridium metal on alumina has been previously investigated
and shown to produce methane as the major product as well as minor
amounts of ethane, ethylene and methyl chloride.40 The formation of
methyl chloride in the Ir/Al2C>3 system was found to be due to the
presence of chloride ions on the alumina surface after impregnation
of the metal halide.70
Lamb and Gates71 have reported that magnesia supported
H20s(00)4 is active for the catalytic hydrogenation of carbon
monoxide to yield to C4 alkanes. The rate of formation of
methane was reported to be 4.2 x 10“4 mol hydrocarixon/mol Os/s at
275°C and 10 atm. The rate of formation of the C2-C4 products was
reported to be 5 x 10-5 to 7 x 10“7 mol hydrocarbon/mol Os/s. The
supported iridium carbonyl systems reported here are less active
(8xl0-5 to 9xl0-6 mol methyl chloride/mol lr4(00) 12) but more
selective.
In this iridium system it is proposed that the methyl chloride
is being formed by the catalytic reduction of carbon monoxide or
frem a stoichiometric decomposition reaction involving the original
cluster. Wider the conditions, the curve in Figure 2-8 would have
to be investigated for over 1000 hours at the activity level seen at
forty hours in order to exhaust all of the CD originally present in
the cluster. Even from the data reported for similar systems71'5 it
is difficult to differentiate between the occurrence of catalytic CD

55
reduction and cluster decomposition. Experiments with labelled 00
have been shown not to be definitive46 for exchange of 00 with the
clusters and intermediates formed in their decomposition could occur
and lead to labelled carbon products. A discussion of the proposed
mechanism for reduction of 00 in the supported iridium systems
reported here is found in a latter section.
Infrared Investigation of Deposited Ir^ (00) After Reaction with
H2. 00 and HClkh
Infrared spectroscopy was used to investigate the alumina and
silica supported tetrairidium carbonyl clusters after reaction with
H2, CD and HC1 at 125°C. The infrared spectrum of Al203/Ir4 (00) 12
arri Si02/Ir4 (00) 12 after exposure to the reactant gases is shown in
Figure 2-9 and the major V qq bands are listed in Table 2-6. A
comparison with the original spectrum shewn in Figure 2-5 indicates
that significant changes in the carbonyl region have occurred. The
decrease in intensity of the 2062 and 2022 cm-1 peaks of lr4(00)12
attributable to the tetrairidium carbonyl cluster indicates that
most of the Ir4 (CD) 12 cluster has decomposed. As can be seen in
Figure 2-9 two strong absorbances at 2140 and 2080 cm-1 appear.
This spectrum is attributed to decomposition of Ir4(C0)12 to lower
rruclearity iridium chlorocarbonyl species.
Decomposition of Al203/Ir4 (CD) 12 is believed to be initiated by
reaction at catalytic conditions of the support surface hydroxyl
groups with the carbonyl groups of Ir4 (CD) 12 as reported by Tanaka
et al.60 and shown in Equation 2-20. In their infrared study of the
decomposition of Ir4(CD)p2 on Al2C>3 no absorbences at wavenumbers

Vo TRANSMISSION
56
Figure 2-9. Infrared Spectra of Deposited Ir4 (00) ^
on (A) Silica Gel and (B) Alumina After
Reaction with H2, CO and HCl(g) at 125°C.

57
Table 2-6. Major V (go) Bands in the Infrared Spectra
for Ehosphine Substituted lr4(00)12 and lr4(00)12
After Reaction with H2, 00 and HC1.
Compound
V co* .
(an-1) Ref.
AI2O3- (PHi2 ) 1,2,3Ir4 (°°) 11,10,9
after reaction at
a) 75°C
2150(m), 2102(sh), 2069(S)
2026 (W), 1734(w), 1719 (W)
46
b) 125°C
2137(m), 2069(S), 2026(W)
1990(m), 1734 (W), 1719 (w)
46
c) 200^0
2055(s)
46
Al203/Ir4(00)12 after
reaction at 125°C
2140(S), 2118 (W), 2082(S)
2022(vw), 1997 (W)
Al2C>3/Ir4 (00) 12/A12C16
after reaction at 125°C
2140(m), 2118 (m), 2075(sh)
2062(S), 2022(m), 1997(m)
A1203/IzC1 (00) 3 after
reaction at 125°C
2118(m), 2075(w), 2062(s)
2022(m), 1997 (w)
Al203/IrCl (00) 3/Al2Cl6
after reaction at 125°C
2113 (m), 2080(w), 2060 (m)
Ir4(00)12/Al2Cl6-NaCl
2190(S), 2160(s), 2125(S)
2112 (m), 1630 (m)
* s=strong, monederate, w^weak, sh=shoulder

58
greater than 2080 can-1 were observed, even after reduction of the
cluster to metallic iridium and subsequent exposure to carbon
monoxide. The appearance of absorptions at wavenumbers greater than
2080 can”1 in our results (Figure 2-9) suggests the formation of
discrete chloro carbonyl iridium complexes.
Infrared Investigation of Supported Ir^(CP)-¡o-AloClg Complexes After
Reaction with H2. 00 and HClfq)
As previously discussed and shown in Figure 2-9 supported
Ir4(C0)12 on alumina or silica gel supports decomposes to produce
lower nuclearity iridium chlorocarbonyl species exhibiting an
infrared spectrum which is different from the starting material.
This decomposition was proposed to be initiated by interaction of
the carbonyl groups of the cluster with the surface hydroxyl groups.
The possibility of cluster decomposition by interaction with
hydroxyl groups was investigated by reacting the support material
with aluminum chloride. In this case, interactions between the
surface hydroxyl groups and the carbonyl groups of the cluster
should have been greatly reduced as shewn in Equation 2-22. If the
major decomposition mechanism of the supported clusters involves the
displacement of carbonyl ligands by surface hydroxyl groups, the
conversion of these hydroxyl to aluminum chloride groups65 should
not only increase the acidity of the support material, but should
also lead to an increased stability of the supported Ir4(C0)12.
The infrared spectrum of alumina supported Ir4(CO)12 treated
with A12C16 after exposure to H2, 00 and HCl at 125°C is shewn in
Figure 2-10 (see Table 2-6 for a listing of the major V ^ bands).

59
The infrared spectrum of silica supported Ir4 (00) 12/A12C16 i-s found
in Figure 2-11. The 2062 can-1 and 2022 cm-1 peaks indicate that
seme of the original Ir4 (00) 12 cluster is still present. The high
frequency peaks and complexity of the spectrum indicate that the
clusters have undergone transformations to produce stabilized
multinuclear iridium chlorocarbonyl species. The possibility of
minor amounts of small metal particles undetectable by infrared
spectroscopy cannot be ruled out.
In the homogeneous Ir4(00)12-A12C16 previously reported,5
infrared spectroscopy was used to investigate the material after
reaction with H2 and 00. A multiband spectrum in the 2100 cm-1
region (see Table 2-6) was found as well as a peak at 1630 cm-1. It
was previously proposed that the lew frequency peak was
characteristic for M^-CO-Lewis acid bonding. In the heterogeneous
Ir4 (00) 12/A12C16 system studies here, no bands in the 1900-1600 cm-1
region were observed. It is possible that absorbances corresponding
to bridging carbonyl groups are present but are either too weak or
masked by absorbances from the support. Alumina does exhibit a
strong absorbance at 1630 cm-1.
Final evidence suggesting the existence of several iridium
chlorocarbonyl complexes was provided by photoelectron spectroscopy
(ESCA). The materials were investigated before and after reaction
with the gases. The results are shewn in Figure 2-12. At best the
results are qualitative. The data obtained from samples of the
supported clusters after exposure to the reactant gases at 125°C
suggested the presence of at least two different oxidation states in

% TRANSMISSION
60
Figure 2-10. Infrared Spectrum of Al203/Ir4 (00) 12/A12C16
After Reaction with H2, 00 and HCl(g) at 125 C.

% TRANSMISSION
61
Figure 2-11. Infrared Spectrum of Si02/Ir4 (00) 12/A12C16
After Reaction with H2, 00 and HCl(g) at 125°C.

62
Figure 2-12. ESCA of SiO^I^ (00) 12/A12C16
(A) Before and (B) After Reaction
with H2, 00 and HCl(g) at 125°C.

63
the resulting iridium complexes as indicated by a minor shift to
higher binding energy.
Investigation of Supported IrCl(00)3 Upon Reaction with H2. 00 and
HC1M
Coliman et al.6 reported that the mononuclear complex,
IrCl(00)3, was either the active catalyst or catalytic precursor
for 00 conversion in the homogeneous Ir4(00)i2/Al2Cl6-NaCl melt
system. In order to gain further insight into what transformations
occurred in the supported iridium systems and the nature of the
inactive iridium species which may have been formed during reaction
with H2, 00 and HC1, an investigation of supported IrCl(OO)3 was
undertaken. IrCl(00)3 was deposited onto A^O^j (see Figure 2-13A).
Upon exposure of A^O^IrCl (00) 3 to H2, 00 and HOI at 125°C only
minor amounts of methyl chloride were formed. The infrared spectrum
of deposited lrCl(00)3 after exposure to H2, 00 and HC1 at 125°C is
shewn in Figure 13B and the major bands are listed in Table 2-6.
The four band pattern present in supported Ir4 (00) 12 (see Figures 2-
5 and 2-6) and Al203/Ir4(00)12/Al2Cl6 after exposure to H2, 00 and
HOI (Figure 2-10) is also present in Al203/IrCl(00)3 after exposure
to the gases.
Fhysisorbed Rhg(OO) is easily formed on the surface of a
support by reaction of Rh(I) surface species with 00 in the presence
of a partial pressure of water.72 Chini and Martinengo73 also
O
reported that Rhg(00)16 was easily synthesized by reaction of
[Eh (00) 2C1]2 with 00 in the presence of water under slightly basic

64
WAVENUMBERS (CM*1)
Figure 2-13. Infrared Spectrum of A^OyTrCl (CD) 3
(A) Before and (B) After Reaction
with H2, C30 and HCl(g) at 125°C.

65
conditions. Recently, ruthenium and osmium carbonyl clusters have
been prepared by the conversion of supported mononuclear halide
complexes (RuCl3 and H20sCl6 respectively) under conditions of
catalytic hydrogenation of carbon monoxide.74 It is believed that
similar chemistry could occur with the supported IrCl(OO) 3 system.
The mononuclear complex could interact with surface hydroxyl groups
of the alumina support under the conditions of 00 hydrogenation
employed resulting in the formation of a higher nuclearity iridium
carbonyl complex. This type of reaction could result in the
formation of an iridium carbonyl cluster exhibiting an infrared
spectrum similar to Ir4(CO)12 (see Figures 2-5 and 2-6).
Deposited IrCl(OO) 3 was also reacted with A12C16 (see Figure 2-
14A) and investigated as a catalyst or catalyst precursor. The
2071 cm-1 peak has replaced the broad absorption in Figure 2-13A
and is attributed to surface molecules of IrCl(OO)3 undergoing a
discrete interaction with bound A1C12 species instead of a variety
of surface acid sites. Upon exposure of Al203/IrCl(00)3/Al2Cl6 to
H2, 00 and HC1 at 125°C only minor amounts of methyl chloride were
formed similar to Al203/IrCl(00)3. The infrared spectrum of
Al203/IrCl(00)3/Al2Cl6 after exposure to H2, 00 and HC1 (shown in
Figure 14B) and the major V qq bands listed in Table 2-6) contains
high frequency absorptions at 2113 and 2060 cm”1 similar to
Al203/IrCl(00)3 after exposure to the gases (see Figure 2-13B) but
does not contain any substantial absorptions belcw 2060 cm-1. They
could be present but are obscured by broad absorptions. The
differences in reactivity for 00 reduction of the supported

% TRANSMISSION
66
A
Figure 2-14. Infrared Spectrum of A^C^j/IrCl (CD) 3/Al2Cl6
(A) Before and (B) After Reaction
with H2, CO and HCl(g) at 125°C.

67
mononuclear iridium chloro carbonyl complexes compared to their
homogeneous analog suggest that their chemical reactivities have
been greatly altered upon heterogenizing them.
Investigation of Metallic Iridium Upon Reaction with H2. 00 and
HCl(q)
Either Ir4 (CD) 12 or IrCl3 3H20 was physically adsorbed onto
alumina. Each sample was pretreated by calcination at 250°q under
hydrogen for five hours. The resulting gray supports were
investigated for catalytic activity upon reaction with H2, 00 and
HC1 and were observed to produce only a trace amount of methyl
chloride at 125°C under H2, 00 and HC1 in a stagnant reactor. An
increase in activity to approximately 2.5 x 10-7 mol CH3CI/ mol Ir/
s was observed for these metallic iridium systems upon raising the
reaction temperature to 200°C. The catalytic formation of
halogenated hydrocarbons from synthesis gas and HCl(g) over
inorganic oxide supported iridium metal between 200 - 1000°C has
previously been reported.40
The infrared spectra observed for the metallic iridium systems
exposed to H2, CD and HC1 was observed to contain one broad weak
absorption whose location was dependent upon the extent of metal
loading. The spectra resembled the spectrum of the decomposed
phosphine supported cluster resulting from exposure to the reactant
gases at 200°C as previously reported.46 The predominant infrared
absorptions assigned for carbon monoxide absorption onto an iridium
metal surface has been reported to range from 2010 cm-1 at low metal
coverage to 2093 cm-1 at metal saturation.75-77
It was previously

68
concluded frcm the similarities in the infrared spectra of metallic
iridium and the decomposed phosphine supported clusters that
metallic iridium is formed above 200°C under a H2, CD and HCl
atmosphere (see Table 2-6). However, below 200°C the stabilization
of discrete iridium complexes is indicated by the complexity of the
infrared spectra.46 The results of this infrared study conducted
with the supported Ir4 (00) 12-A12C16 materials after reaction with
H2, CD and HCl suggest that discrete iridium complexes have also
been stabilized on the support. A variety of iridium dhlorocarbonyl
complexes have been reported to be formed by the reaction of
powdered iridium metal with 00 and Cl" ions.78 The possible role of
these stabilized iridium complexes in the reduction of carbon
monoxide is discussed in the mechanism for 00 reduction found in a
later section.
Investigation of Other Lewis Acids
Other Lewis acids were investigated for the preparation of an
Ir4(00)12-Lewis acid solid material capable of catalytically
hydrogenating carbon monoxide with HCl to methyl chloride. The
acids investigated were FeCl3, A1BT3 and SbCls- The activity
observed when the other Lewis acids were investigated was less than
that observed for the aluminum chloride treated material. For the
material treated with iron chloride the conversión of the iron
chloride to iron carbonyl is believed to occur in the presence of
the carbon monoxide reactant gas. This is followed by loss of the
iron carbonyl from the system as indicated from a noticeable yellow

69
coloration of a post bubbler in the flew system. This type of
reaction is not unreasonable considering the volatility of iron
pentacarbonyl. In the case of the aluminum bromide treated iridium
clusters the conversion of the bromide complex to the chloride
complex is believed to occur in the presence of HC1. Even in
these systems the activity for the formation of methyl chloride was
less than the analogous solids prepared form aluminum chloride. The
antimony pentachloride treated materials exhibited the highest
activity for the formation of methyl chloride of the three
alternative acids employed. During the course of the reaction with
H2, 00 and HC1 the formation of metal was observed to occur. This
was evident from plating out of a black mirrored ring above the
solid material in the reactor tube. Attempts to increase the
activity and stability of these systems (by varying the reaction
temperature and amount of added HC1) for the reduction of carbon
monoxide were unsuccessful.
Investigation of A^Clg Treated Commercial 00 Reduction Catalysts
A copper methanol catalyst was investigated for catalytic
activity in the reduction of carbon monoxide with hydrogen and
hydrogen chloride to produce methyl chloride. The Lew Temperature
Shift catalyst (United Catalyst) did not exhibit any activity for
the reduction of carbon monoxide under the reaction conditions
employed even at temperatures of 200°C. These result are not
surprising because the materials are reported to exhibit activity at
220-210°C and 50-100 atmosphere pressure.79

70
Upon treatment with aluminum chloride these materials did
exhibit activity for the formation of methyl chloride. The activity
of these catalysts was '10”10 mol O^Cl/s/g catalyst which is
similar to that observed for the previously described supported
Ir4 (CO) i2“Al2Cl6 systems. The observed activity for the reduction
of carbon monoxide under mild conditions with the methanol catalysts
is attributed to the bifunctional activation of carbon monoxide
occurring upon treatment with aluminum chloride.
The lifetime of the treated methanol catalysts was observed to
be approximately 8-15 hours depending upon the amount of HC1
reactant gas and the flew rates. A color change in these materials
from brown-black to dark green is accompanied by a decrease in
activity. It is suspected that the decrease in activity is a result
of the formation of copper chloride. These methanol catalyst have
been reported to be sensitive to poisoning by HC1 leading to the
formation of copper chloride79 as shewn in Equation 2-25.
CU-O-Zn + HC1 > CuCl + HOZn (2-25)
Accompanying this change is the accumulation of water in the reactor
tube which leads to the conversion of aluminum chloride to aluminum
hydroxide decreasing any lewis acid interactions. Several
experiments were conducted to try to increase the stability and
activity of these systems for the formation of methyl chloride
including varying the amount of HC1 present as a reactant and
temperature. In all cases the activity of the system would decrease

71
accompanying a color change in the catalysts. It is proposed that
the activity displayed by these systems is due to the Lewis acid
treatment leading to mild reduction of carbon monoxide via a
bifunctional activation mechanism.
Mechanism Proposed for the Formation of Methvl Chloride
A schematic representation summarizing the reaction of H2, CO
and HC1 with all the various supported iridium carbonyl complexes is
shown in Figure 2-15. A series of control reactions completed in
this work support the formation of methyl chloride from organic
residues introduced onto the supported phosphine substituted iridium
ccnplexes during preparation. An infrared study previously
conducted by Weiss46 of these materials before and after reaction
established that decomposition of the phosphine substituted clusters
to lower nuclearity iridium species occurred during the formation of
methyl chloride.
In this work, tetrairidium carbonyl clusters were deposited
onto inorganic oxide supports. These materials were then treated
with aluminum chloride and shown to undergo interactions with Lewis
acid sites present on the surface of the support. Evidence for
these interactions was provided by the presence of new absorbances
in the carbonyl region as indicated by infrared spectroscopy. The
deposited Ir4 (CD) 12 clusters were found to react with H2, CD and HCl
to produce methyl chloride as the major product detected in the post
gas stream. The formation of methane, trace C2 products, water and
carbon dioxide was also detected. The aluminum chloride treated

72
lr*Cly(CO)z
Hz/CO/HCI
200°C
METALLIC IRIDIUM
(I r )n — CO
Figure 2-15. Proposed Mechanism for the Formation
of Methyl Chloride with the Supported
Iridium Carbonyl Clusters.

73
materials were found to be approximately two orders of magnitude
more active for the formation of methyl chloride than the analogous
materials which were not treated with the Lewis acid.
Studies of the deposited iridium clusters after exposure to the
reactant gases indicate that decomposition of the iridium clusters
has occurred during the course of reaction. Infrared spectroscopy
supports the deccnposition of the clusters to lower nuclearity
iridium chloro carbonyl species and not to metallic iridium. These
resulting iridium species which are formed during reaction are
eventually inactive for the reduction of carbon monoxide. At
elevated temperatures (>200°C) further decomposition to metallic
iridium is observed. The supported metallic iridium materials
exhibit minor activity upon reaction with H2, 00 and HC1 for the
formation of 02-03 hydrocarbons and methyl chloride. The formation
of methyl chloride at temperatures above 200°C can be explained by a
Fischer-Tropsch mechanism as previously described by Vannice.40
It is proposed that the formation of methyl chloride at
temperatures below 200°C may result frcm a pathway involving the
reduction of carbon monoxide. For the deposited Ir4(00)12 materials
in the absence of the aluminum chloride treatment it is proposed
that the formation of methyl chloride results frcm decomposition of
carbonyl groups present on the original cluster. This reduction is
proposed to be initiated via a decarbonylation mechanism frcm
interaction of the carbonyl groups of the cluster with the hydroxyl
groups of the support (as shown in Equation 2-26)

74
Ir4 (00) 12 + xSOH > Ir4(CX))12_x(SOH)x + xOO (2-26)
followed by subsequent reduction of carbon monoxide to the observed
products. The resulting materials exhibit strong absorbances at
2082 and 2140 an-1 indicative of mononuclear complexes. The
investigation of supported mononuclear IrCl(00)3 for activity for
reduction of carbon monoxide in this work resulted in the formation
of only trace amounts of methyl chloride.
The formation of methyl chloride in the aluminum chloride
treated materials is proposed to be initiated by a bifunctional
activation of carbon monoxide via interaction of the oxygen end of a
bound iridium carbonyl species with aluminum chloride. Subsequent
reaction with H2 and HC1 would lead to the formation of the observed
products. The resulting material after reaction supports the
presence of iridium species which are not mononuclear as indicated
by the complexity of the infrared data. It cannot be ruled out that
decomposition of the supported Ir4 (00) 12-A12C16 materials is not
initiated by interaction of the carbonyl groups of the iridium with
the aluminum chloro present on the surface of the support. It is
proposed that the increased activity for the formation of methyl
chloride for the Lewis acid treated materials is due to the
stabilization of multinuclear iridium species. The stabilization of
multinuclear iridium species in the supported phosphine substituted
iridium complexes were believed to be active for the formation of
methyl chloride in that system.

75
The activity of the deposited iridium carbonyl clusters were
shown to be greater for the formation of methyl chloride than any of
the previously investigated supported iridium systems. Even with
the systems described in this study high levels of activity were not
achieved such that commercial production of methyl chloride based
upen synthesis gas would be attractive.
D. Summary
The investigation of supported phosphine substituted iridium
carbonyl clusters resulted in the identification of organic residues
on the surface of the inorganic oxide support which were
incorporated during preparation. The presence of these residues was
shown to result in the formation of alkyl halides (CH3CH2CI and
CH3CI) upon reaction with H2, 00 and HC1. The results of control
experiments suggest that the previously reported activity for the
formation of methyl chloride from reduction of CO with H2 and HC1 by
these systems were clouded by the presence of carbon sources
introduced during the support functionalization procedure.50
A study was undertaken whereby Ir4 (00) y2 was deposited on to
inorganic oxide supports such as alumina and silica gel and also
treated with aluminum chloride. The characterization of these
supported clusters was conducted by infrared spectroscopy. The data
obtained suggest that Ir4 (00) 12 remains intact upon deposition onto
the oxide supports and exhibit spectral features common to Ir4(CO)12

76
in the solid state and in solution. Upon reaction of the deposited
iridium clusters with aluminum chloride the appearance of high
frequency bands in the infrared spectra of these materials was
observed. These data suggest that the supported iridium carbonyl
clusters have undergone interactions with strong Lewis acid sites
present on the surface of the support.
The supported iridium carbonyl clusters were investigated for
catalytic activity for reaction with H2, CD and HC1 to produce
methyl chloride. Precedence for this reaction is provided from a
report of a homogeneous CD hydrogenation system where methyl
chloride was produced though ethane was the major product reported.
The reported catalyst was Ir4(CD) 12 in a molten Al2Cl6-NaCl
medium.5'6 The mild reaction conditions (1-2 atmosphere pressure
and temperatures below 200°C) necessary for the reduction of carbon
monoxide in the homogeneous system were believed to be due to the
strong Lewis acid solvent where bi functional activation of carbon
monoxide could occur. The supported iridium carbonyl clusters
treated with aluminum chloride are this researcher's version of the
homogeneous Ir4(CD)12-A12C16 system. These materials were
investigated for the reduction of carbon monoxide with H2 and HC1 at
1 atmosphere pressure and 125°C. The supported iridium carbonyl
clusters were found to result in the formation of methyl chloride as
the major product which was quantified, unlike the homogeneous
system where ethane was the major product reported. The formation
of methane, ethane/ethylene, acetaldehyde, ethyl chloride, methylene
chloride, carbon dioxide, and water were also detected in the

77
supported Ir4(00)i2-Al2Cl6 system. The Lewis acid treated materials
were found to exhibit approximately two order of magnitude greater
activity than the iridium clusters deposited on alumina. The high
selectivity for the formation of methyl chloride in the supported
system is attributed to the presence of the HC1 in the reactant
gases which would convert C3 intermediates to methyl chloride prior
to homologation and hydrogenation.
In the homogeneous system IrCl(00)3 was also preposed to be an
active catalyst or catalyst precursor.6 Investigation of this
supported mononuclear complex both in the absence and presence of
aluminum chloride resulted in the formation of only minor amounts of
methyl chloride upon reaction with H2, CD and HC1. The formation of
methyl chloride has also been previously reported from the reaction
of H2, 00 and HC1 over supported metallic iridium.40 The
investigation of metallic iridium as a catalyst for the reduction of
carbon monoxide to methyl chloride resulted in only trace amounts of
methyl chloride below 200°C in a stagnant reactor while above 200°C
the activity was observed to increase. It is proposed that metallic
iridium is not responsible for the observed formation of methyl
chloride in the supported Ir4 (00) 12-A12C16 system and that
stabilization of a discrete iridium complex active for methyl
chloride formation occurs.
The supported iridium clusters were investigated by infrared
spectroscopy after reaction with H2, 00 and HC1. The materials
investigated were no longer active for reduction of carbon monoxide.
Iridium carbonyl on alumina or silica gel is proposed to decompose

78
to mononuclear iridium chlorocarbonyl complexes as indicated by
infrared data. A decarbonylation reaction whereby interaction of
the bound carbonyl groups of the cluster may interact with hydroxyl
groups cxi the surface of the support is believed to result in
decomposition of the cluster. Infrared investigation of the
aluminum chloride treated iridium clusters after reaction revealed
complex spectra which are attributed to the presence of stabilized
multinuclear and not metallic iridium. Similar complex infrared
data was obtained in the previously studied46 phosphine substituted
clusters which were proposed to be multinuclear iridium
chlorocarbonyl species. The decomposition of supported Ir4 (00) 12-
A12C16 via interaction with surface A1C12 grcxps formed upon
treatment with aluminum chloride and the presence of small amounts
of iridium metal undetected by infrared spectroscopy cannot be ruled
out.
In the phosphine substituted and the aluminum chloride treated
iridium carbonyl systems data suggest that catalytic reduction of
carbon monoxide is not the major pathway which would account for the
formation of methyl chloride. Discarding the presence of organic
residues in the supported systems the major route for the formation
of methyl chloride appears to be one comprising of the decomposition
of the carbonyl groups originally present on the lr4(00)12 clusters.
The inability to form and stabilize an active heterogeneous analog
of the homogeneous Ir4 (CD) 12-A12C16 system from lr4(00)12 or
IrCl(00)3 suggests that alterations of the active environments have
occurred in the heterogenized system during catalysis.

III. RHODIUM PERFLUOROGARBOXYIATE
TRIHffiNYLFHOSFHINE OCMPLEXES PC®
OIEFIN HYEROPOFMYIATIC®
A. Background
Metal carboxylate dimers have been the subject of many
reviews.80-82 The investigation of these complexes is of interest
since they can act as model compounds for the study of metal
synergism. These dinuclear complexes contain metal-metal bonds and
four bridging carboxylate ligands resulting in a "lantern
structure." Rhodium(II) carboxylates of the general formula
Rh2(°2CR)4/ possess a rhodium-rhodium single bond and readily form
adducts, in which the axial positions are occupied by solvents or
ligands.
The reactivity of rhodium (II) carboxylates with a variety of
donor ligands has been widely investigated.83-89 Drago and
coworkers have measured equilibrium constants and enthalpy of
coordination for various axial ligands.83»86 The formation of 1:1
and 2:1 ligand to dimer complexes has been observed. Once the 1:1
adduct has been formed, the second axial ligand is less strongly
bound at the second rhodium center.84 Studies have established that
electron withdrawal frcm rhodium (II) perfluorocarboxylate complexes
enhances the Lewis acidity of the axial coordination sites. Fully
fluorinated rhodium (II) tetrakis (heptafluorobutyrate) has greater
79

80
covalent and electrostatic sigma acceptor properties than the
corresponding butyrate complex. Research has also focused on the
influence of base coordination at one rhodium center on the
stretching frequency of coordinated CD at the second metal center.85
The coordination chemistry of rhodium (II) carboxylates has also
been extended to include olefins. Spectroscopic studies conducted
by Doyle et al. yielded the first demonstration of olefin
coordination with rhodium(II) perfluorocarboxylate complexes.87
Equilibrium constants were reported for the 1:1 adducts of
Rh2(O2OCF3)4 with a series of alkenes. No spectroscopic evidence
for the binding of alkenes by rhodium (II) acetate in solution was
obtained in Doyle's study. These results are in contrast to those
reported by Schurig where equilibrium constants for olefin-
rhodium (II) acetate adducts have been determined from retention data
by ccnplexation gas chromatography rather than from spectroscopic
studies.88
The olefin coordination chemistry of rhodium (II)
perfluorocarboxylates in solution has been extended by Doyle et al.
to include rhodium(II) tetrakis (heptafluorcbutyrate).89 Equilibrium
constants for 1:1 complexes between rhodium (II) perfluorobutyrate
are approximately three times greater than those determined for
rhodium (II) trifluoroacetate. The increased ability of the
fluorinated rhodium (II) carboxylates to coordinate molecules is
attributed to the increased Lewis acidity of the rhodium center due
to the electron-withdrawing properties of the fluorinated
carboxylate ligands. Based upon these findings, rhodium

81
carbaxy lates would be expected to exhibit activity in catalytic
reactions involving the binding and subsequent activation of
molecules such as olefins, carbon monoxide, etc.
Rhodium(II) acetate has been reported to be an active catalyst
for the homogeneous hydrogenation of olefins in a wide variety of
solvents.90'91 A mechanism has been proposed which involves the
intact dimer and heterolytic cleavage of dihydrogen92 as shown below
in Equation 3-1. Terminal olefins have been shewn to undergo 15-20%
+H2 +l
Rh2 (QAc) 4 > HEh(QAc) 3Rh >
HOAc (3-1)
(HL)Rh(QAc) 3Rh > H2L + Rh2(QAc)4
isomerization while the catalyst is less active or inactive for
internal olefins.
The cyclopropanation of diazoesters to alkenes to yield
cyclcpropanes has also been reported to most effectively be
catalyzed by rhodium(II) carboxylates93'94 as shewn in Equation
3-2. The cyclopropane carboxylic acid ester products have use as
v1 /
crc
/ \
r3
R2 R4
R1 R3
Rh2 (C^CR) 4 \ /
+ No = CH-OOOR > C —C
/\/\
r2 c R4
/ \
H COOR
(3-2)

82
insecticides. Mechanistically, a Rh2 (O2CR) 4-carbene complex is
proposed which then transfers the carbene to the substrate.95 In
the presence of rhodium(II) carboxylates and vanadium or molybdenum
compounds cyclohexene can be oxidized to give 1,2 epoxycyclohexene-
3-ol.96 The reaction takes place at 55°C under 1 atm. of oxygen and
proceeds via a cyclohexyl hydroperoxide intermediate. Ihe best
results have been reported for fluorinated carboxylate ligands such
as trifluoroacetate.97 Rhodium(II) carboxylates react in methanolic
HBF4 in the presence of trifhenylphosphine and lithium carboxylate
to produce Rh^CR) (PPh3)3.98 These complexes have been reported to
catalyze the homogeneous hydrogenation of alkenes and alkynes.
Rhodium(II) carboxylates have received attention as second
generation platinum metal anticancer corpounds. The use of these
complexes was first reported by Bear in 1972.99 Investigation into
the chemical properties and biological effects of rhodium (II)
carboxylates in relationship to their ability to bind unprotonated
amino and sulphydryl groups have been conducted. Invivo studies
have shown that rhodium carboxylates are able to inhibit certain
biological processes in particular the cellular synthesis of DNA
While these ccnplexes have been studied as catalysts for some
reactions as discussed above, the fluorinated dimers have not been
extensively investigated. The reported increased ability of the
fluorinated rhodium carboxylates to bind molecules such as olefins
and 00 would be expected to render these complexes active catalysts
for reactions such as hydrof ormylations.

83
Hie hydroformylation reaction was discovered by 0. Roelen in
1938 while studying the effect of added olefins in the Fischer-
Tropsch Process.100 Later studies concluded that the presence of
cobalt in the heterogeneous Fischer Tropsch catalyst was catalyzing
the hydroformylation reaction and that the actual catalyst was
homogeneous.101 The hydroformylation or " oxo" reaction is the
reaction of synthesis gas with an olefin102 as shown in Equation
3-3. In the absence of a catalyst the reaction does not proceed.
catalyst
H2 + 00 + RCH CH2 > RCH2CH2CHO + RCH(CH0)CH3
(3-3)
The products from the hydroformylation reaction are aldehydes. Both
the linear and branched aldehyde may be formed. Linear aldehydes
have the greatest chemical utility. The addition of bulky phosphine
ligands to hydroformylation catalysts results in an increase in the
selectivity for the formation of the linear aldehyde. Byproducts
commonly formed during hydroformylations include alkanes and
alcohols.
Bie production of butyraldehyde from the reaction of H2, CO and
propylene is the largest commercial application of the
hydroformylation process.103 Approximately 6 billion pounds of
butyraldehyde are produced annually. Bie condensation arid
hydrogenation of the aldehydes ultimately yields alcohols which are
used as ccnpanerrts of plasticizers. An additional 2-6 billion
pounds of other aldehydes are also produced annually by the
hydroformylation process. The ultimate products are long chain

84
alcohols which have application in the production of biodegradable
soaps, detergents, and as components of plasticizers.
Two aspects of the hydroformylation reaction are of industrial
importance. One involves the formation of undesirable byproducts
which should be minimized during reaction. The other aspect
concerns the development of processes which avoid expensive
operating conditions which occur when high pressures and
temperatures are employed to carry out the reaction. Commercial
processes have been developed based upen both cobalt and rhodium
catalysts with each having their own advantages and
disadvantages.104
Cobalt hydroformylation processes typically employ dicobalt
octacarbonyl, Co2(OD)8, as the catalyst precursor.105 The active
catalyst is HCo(OO) 4 which is a volatile, unstable complex that is
difficult to separate from the reaction products and recycle into
the system. Processes based upon hydrido cobalt catalysts typically
operate under severe reaction conditions. Reaction pressures of
200-350 atmospheres and temperatures between 150-200°C are generally
employed. The product isomer ratio obtained with hydrido cobalt
catalysts is approximately 3 or 4:1 (mol linear : mol branched
aldehyde product). The high reaction pressures and temperatures
used to stabilize these complexes promote the formation of
byproducts.
Fhosphine modified hydrido cobalt catalysts have also been
developed for the hydroformylation of olefins.106 These systems
usually result in the complete reduction of the aldehyde to the

85
alcohol. The phosphine used is tributylphosphine and the active
catalytic species is proposed to be HCo(OO)3(PBu3). The phosphine
modified system is less active for hydroforrnylation but much more
active for hydrogenation and generally results in a linear :
branched alcohol ratio of 7:1. This catalyst is more stable than
the unmodified catalysts resulting in lower reaction pressures of
100 atmospheres.
Ccnmercial hydroforrnylation processes have recently been
developed based upen rhodium.107 Much milder reaction conditions
are used with the rhodium systems compared to any of the cobalt
systems and rhodium has an activity 104 times greater than that of
cobalt. Reaction pressures of 10-25 atmospheres and temperatures
around 100°C are generally employed, ihosphine modified hydrido
rhodium complexes, such RhH(OO) (FEh3)3,108'109 are used as
catalysts. Excess triphenylphosphine is added to increase the
product selectivity for the formation of the linear aldehyde while
decreasing the rate of hydroforrnylation. The reaction has even been
conducted in molten triphenylphosphine.110 Despite the high
activity and selectivity and milder reaction conditions employed
with modified rhodium catalysts, the high cost of rhodium and
recovery problems has limited their use. The development of
homogeneous rhodium systems or heterogeneous systems which exhibit
greater activity and selectivity than those currently employed and
operate under milder reaction conditions may offset seme of the
disadvantages associated with current rhodium systems.

86
The proposed mechanism for the hydrofonnylation of olefins with
phosphine modified rhodium catalysts is similar to that proposed
with cobalt catalysts.111 The mechanism of the hydrofonnylation
reaction catalyzed by phosphine modified rhodium systems has been
the subject of many review articles.102'112»113 In the modified
rhodium systems, the immediate catalyst precursor is RhH(CO) (PPh3)3.
To create a vacant coordination site on the rhodium center,
phosphine dissociation is proposed to occur as shewn in Equation 3-
4. The decrease in activity encountered upen addition of excess
triphenylphosphine to hydrido rhodium hydrofonnylation
HRh(OO) (PFh3)3 < > HRh(OO) (PFh3)2 + Pih3 (3-4)
catalysts is believed to be a result of driving the equilibrium in
Equation 3-4 toward the side of the tris (phosphine) complex. Other
investigators have proposed that the addition of phosphine inhibits
a similar dissociation reaction114»115 as shewn in Equation 3-5.
Either of the coordinatively unsaturated rhodium hydrido complexes
in Equations 3-4 and 3-5 may then coordinate olefin.
HRh(OO) 2 (PFh3) 2 < > HEh(00) 2(1^3) + Pih3 (3-5)
The mode of olefin coordination across the rhexiium-hydride bond
ultimately determines the product selectivity for the formation of
linear or branched aldehydes. Markovnikov addition of the olefin
across the Eh-H bend results in the formation of a branched alkyl
intermediate and eventually the branched aldehyde. Anti-markovnikov
addition of the olefin across the Kh-H bond leads to the formation

87
of the linear alkyl intermediate and then the linear aldehyde
product. The next step preposed in the hydroformylation mechanism
is 00 migratory insertion to form an acyl species,
Rh(00) (acyl) (PFh3)2. This is followed by oxidative-addition of H2
at the rhodium center to yield a Rh(III) dihydrido acyl complex
which may then reductively eliminate the aldehyde product. Addition
of dihydrogen is proposed the be the rate-determining step.103
Others have proposed that the formation of the alkyl complex from
the trans bis (triphenylphosphine) complex is rate determining.116
After elimination of the product the remaining rhodium complex is
KhH(OO) (PEh3)2 which may then react with 00 to complete the catalyst
cycle. The formation of byproducts results from direct
hydrogenation of the alkyl intermediate to form the alkane or from
hydrogenation of coordinated aldehyde to yield the alcohol.
Mechanistic studies have shewn that many complexes exist in
solution during hydroformylation with phosphine modified
catalysts.117 Seme of the active catalysts or catalyst precursors
are RhH(OO) (PEh3)3, KhH(00)2(FFh3)2, RhH(00)2(PFh3), and
RhH(CO) (Pfh3)2 which exist in equilibria with each other via a
series of ligand exchange or dissociative reactions. The key
intermediate species is KhH(00)2(PFh3)2. Dinuclear rhodium
complexes such as [Rh(CD)2(PFh3)2]2 have been shown to be inactive
as catalysts for hydroformylations.118 The presence of excess
triphenylphosphine and hydrogen is believed to suppress the
formation of these dimers by driving the equilibrium in Equation 3-6
to the left. While a general mechanism for rhodium-catalyzed

88
FFh3, H2
2RhH(00) (FFh3)3 < > [Fh(00)(EBl3)2]2 (3-6)
hydroformylation is understood, the exact number of coordinated
phosphines and carbonyl groups on the active species is still
debated. More than one active species probably exists in solution.
Based upen the reports described above there are still areas in
hydroformylation chemistry for the development of catalysts which
exhibit higher activity and selectivity than existing systems and
operate under milder reaction conditions. The family of rhodium(II)
carboxylates should exhibit activity for the hydroformylation of
olefins in view of their ability to bind olefins, CD and activate
H2. The increased Lewis acidity of the rhodium centers resulting
frem the fluorinated carboxylate ligands should render these
complexes as active catalysts or catalyst precursors for the
hydroformylation of olefins. The study of the reactivity of these
complexes could result in the investigation of new catalytic
species. A detailed study of the use of fluorinated rhodium(II)
carboxylates as catalysts for hydroformylations is warranted.
B. Experimental
Reagents
KhCl3*3H20 and RhCl(CD) (PFh3)2 were purchased from Strem
Chemical Company. Triphenylphosphine was purchased from Aldrich
Chemical Company. Sodium acetate and potassium hydroxide were

89
purchased from Fisher Scientific. These materials were used as
purchased unless otherwise stated. Acetic acid , acetic anhydride,
butyric acid, butyric anhydride, trifluoroaoetic acid,
trifluoroaoetic anhydride, heptafluorobutyric acid and
heptafluorobutyric anhydride were purchased from Aldirch Chemical
Company and used without further purification. Nafion, a
fluorocarbon polymer was a gift from E.I. du Fait de Nemours & Co.
Solvents were dried by distillation over CaH2 or P2C>5 and stored
over 4°A molecular sieves. 1-Hexene, styrene, and ethyl vinyl ether
were passed through a column of activated Alcoa alumina prior to
use.
Hydrogen was purchased from Aireo. Carbol monoxide (CP grade
99.5%) was purchased from Matheson Gas Products. Isotopically
enriched carbon monoxide (25% 1300, 75% 1200) was purchased from
Isotec Incorporated. All gases were used without further
purification.
Instrumentation
All air sensitive manipulations were performed using Schlenk
technique. All syntheses were performed under a nitrogen or carbon
monoxide atmosphere. Infrared spectra were obtained either as Nujol
mulls or in dichlorcmethane solution by using a Nicolet model 5DXB
spectrometer. NMR spectra were obtained by using a Varian 300XR
spectrometer. Visible spectra were obtained by using a Perkin-
Elmer model 330 spectrophotometer with matched quartz 1.0 cm. cells.
Elemented, analyses were performed by the Microanalytical Laboratory,

90
University of Florida, Gainesville, Florida. Gas chromatographic
analyses were performed by using a FID Varian model 3300
chromatograph equipped with a 1/8 inch x 8 foot stainless steel
column containing 15% DEGS on Chrcmosorb W AW. The column
tenperature was maintained at 100°C. GC FEER analyses were
performed by using a Nicolet 5DXB spectrometer equipped with a
Nioolet Interface and a Hewlett-Packard 5890A gas chromatograph with
a 1.5 micrometer x 30 meter DB130 fused silica capillary column. GC
MS analyses were performed by using a Finnigan Mat 700 Ion Trap
detector system 3.00 with an IEM AT data station. The system was
connected to a Varian model 3400 gas chromatograph equipped with a
0.25um x 60m SPB-1 capillary column. All liquid phase
hydroformylation reactions were carried out in a 100 mL pressure
bottle equipped with a stainless steel Swaglok pressure head similar
to that previously described by Zuzich119 as shewn in Figure 3-1.
Synthesis of Tetrakis(acetato) Dirhodiumdl). Rh2 (°2CCH3^ \
Tetrakis (acetato) dirhodium (II) was prepared from EhCl3* 3H20
according to a method of Legzdins et al.120 EhCl3 H20 is dissolved
in ethanol with Na02CCH3 and CH3000H. The initial red solution
changes to dark green upon refluxing for approximately 1 hour. The
green solid (crude rhodium acetate) that precipitates is
recrystallized frem methanol, yielding the bluish-green methanol
adduct. Upon heating under vacuum for 12-15 hours pure emerald
green rhodium acetate dimer, Rh2(OAc)4, is obtained. %C 21.67 found
(21.71 calc.), %H 2.61 found (2.71 calc.).

91
1/4" Silicone
Sceptum
Figure 3-1. A Diagram of the Pressure Bottle Apparatus
Used for the Hydroformylatian Reactions.

I
92
Synthesis of Tetrakis (perfluorobutvrato) Dirhodium(II).
Hi2ÍQ20C3F7i4
Rhodium acetate is converted to tetrakis (perfluorcbutyrato)
dirhodium(II) according to a method reported by Drago et al.83 by
refluxing rhodium acetate dimer in heptafluorobutyric acid and
heptafluorobutyric anhydride (10:1 by volume) for approximately 1
hour under a nitrogen atmosphere. The volume is reduced to '80% and
the crude rhodium (II) perfluorobutyrate dimer is recrystallized from
benzene and washed with cold pentane. The green product was dried
under vacuum at 100°C for 12-15 hours to give pure green-yellow
rhodium (II) perfluorobutyrate dimer, Rh2(pfb)4. Rh2 (O2CC3F7) 4 2H20
%C 17.50 found (17.55 calc.) %H 0.00 found (0.36 calc.).
Synthesis of Other Rhodiumill) Carboxvlate Dimers
Rhodium(II) butyrate and rhodium(II) trifluoroacetate were
prepared by a similar method employed for the synthesis of rhodium
(II) perfluorobutyrate. An appropriate amount of rhodium(II)
acetate was added to a solution containing the neat acid and
anhydride (10:1 by volume) and allowed to exchange at reflux for 1
hour. The volume was reduced and the crude complex allowed to
recrystallize from benzene, collected by vacuum filtration and
washed with cold pentane. The complexes were dried under vacuum
prior to use.

93
Preparation of Trifluoroacetato Tris(triphenylphosphine) RhodiumfI).
RhfCbCCFj) from Rhodium(II) Trifluoroacetate
Trifluoroaoetatotris (triphenylphoshine) rhodium (I),
Ki(02CX3:’3) (FFt^) 3, was prepared from Rh2(02CCF3)4 according to a
method similar to that reported by Tel ser and Drago.121'122
Rhodium(II) trifluoroacetate (0.162g, 0.246 nmol) was dissolved in 5
mL toluene. Triphenylphosphine (0.640g, 2.46 nmol) was dissolved in
5 mL toluene and added drqpwise to the Eh^C^CCJ^^ solution. Upon
addition of PFh3 the initial green solution changed to brown and
then to red. The solution was heated for 1 hour during which time
the formation of an orange precipitate was observed. The hot
solution was filtered and washed with toluene. Precaution should be
taken to eliminate oxygen or the formation of triphenylphosphine
oxide is observed. The solid was dried under vacuum at 50°C for 12
hours. The characterization of the complex is discussed in a later
section. Ml(02CXT’3)(PFh3)3 %C 66.84 found (67.07 calc.) %H 4.49
found (4.52 calc.)
Preparation of Trifluoroacetato Tris (triphenylphosphine) Rhodium Cl)
from Hvdrido Tetrakis (triphenylphosphine) Rhodium(I)
Trifluoroacetatotris(triphenylphosphine) rhodium(I) was
prepared from HRh(PFh3) 4. Hydrido tetrakis(triphenylphosphine)
rhodium(I) was prepared from a literature method.123 Hot ethanolic
solutions containing RhCl3 H20 and KDH were added rapidly and
successively to a vigorously stirred, boiling solution of PFh3 in
ethanol. After heating at reflux, yellcw HRh(PEh3)4 is precipitated
from the reaction, collected by filtration and dried under vacuum.

94
Kh(C>2CCF3) (PEI13) 3 was prepared from HRh(FFh3)4 according to a method
reported in the literature.124 Trifluoroacetic acid (0.5 mL) was
added to a suspension of HRh(FFh3)4 (0.29g) in ethanol. The mixture
was heated at reflux for 15 minutes during which time the initial
yel lew suspension changed to brown and finally an orange solid
precipitated. The orange solid, RhfC^CO^) (PE*^) 3, was collected by
filtration and washed successively with methanol, water, methanol
and hexanes. The solid was dried under vacuum at 50°C for 12 hours.
The characterization of this complex is discussed in a later
section. %C 66.43 found (67.07 calc.) %H 4.47 found (4.52 calc.)
Preparation of Trifluoroacetato Bis(triphenvlphosohine) Rhodium m
Carbonvl. KhfOoCCTVOOfFtt^
Trifluoroacetato bis(triphenylphosphine)rhodium(I) carbonyl,
Eh(020CF3)00(FEh3)2, was prepared similar to a method reported in
the literature from RhH(OO) (PPh3)3.124 To a solution containing
0.30g RhH(OO) (PEÍI3) 3 in ethanol was added 0.5 mL trifluoroacetic
acid. The mixture was allowed to stir at reflux for 20 minutes
during which time a yellcw solid precipitated from solution. The
yellcw solid, Ki(C>2CCF3)GO(PFh3) 2 was collected by filtration and
washed successively with methanol, water and methanol then dried
under vacuum at 50°C for 12 hours. %C 60.4 found (60.9 calc.) %H
3.8 found (3.9 calc.)
Preparation of Nafion Supported EhfChOCT^ (FFhj^
A EMF solution containing 0.03g Rh(02CCF3) (PEh3)3 was stirred
with l.Og Nafion-H for 12 hours. The solvent was removed by vacuum

95
and the resulting yellow resin dried under vacuum. Conversion to
the sodium form, Nafion-Na, was done by stirring the resin in 1.0M
Na20C>3 for 5 hours. The resin was filtered, washed with deionized
water and the procedure was repeated.
Hvdroformvlation of Olefins with the Rhodium Complexes
For the hydroformylation experiments approximately 10”5 mol
rhodium complex was placed in a pressure bottle containing 10 mL
(8xl0-2 mol) olefin. Appropriate molar ratios of triphenylphosphine
were added as desired. 2-octanone was used as an internal standard.
A typical reaction was conducted in an oil bath at 100°C with 50
psig H2 and CO in a ratio of 1:1. The liquid products were
monitored by gas chromatography. Turnover numbers, TON, are
expressed as mol product/ mol catalyst. Investigation of the species
formed during the hydroformylation reaction is discussed in the
results section.
C. Results and Discussion
Investigation of Rhodium(II) Perfluorocarboxvlate Complexes as
Catalysts for the Hydroformylation of 1-Hexene
Rhodium(II) perfluorocarboxylate complexes were investigated
for the catalytic liquid phase hydroformylation of 1-hexene using
the pressure bottle apparatus discussed in the experimental section.
As previously reported, the perfluorocarboxylate complexes exhibit
increased ability to bind olefins compared to their nonfluorinated

96
analog.87'89 These reports suggest that the carboxylate complexes
would exhibit reactivity in catalytic reactions involving the
binding and subsequent activation of olefins such as
hydroformylation. Initial studies were conducted using rhodium (II)
perfluorobutyrate, Rh2(pfb)4, and rhodium(II) trifluoroacetate,
Rh2(tfa)4, ccnplexes to catalyze the reaction shown in Equation 3-7.
Upen reaction of hydrogen and carbon monoxide with 1-hexene in the
presence of the rhodium (II) perfluorocarboxylate complexes the
formation of 1-heptaldehyde and 2-methyl hexanal was observed.
Rh(II) Dimer RCH2CHO
H2 + 00 + RCH CH2 > + (3-7)
100°C, 50 psig. RCH(CH0)CH3
The products were identified by gas chromatography as shewn in
Figure 3-2. The formation of hexane was also identified by GC MS.
The use of 25% 1300, 75% 12C0 reactant carbon monoxide resulted in
the incorporation of the labelled reactant into the aldehyde
functionality as shewn in the GC MS in Figure 3-3. The appearance
of (Mfl)+ ion peaks shewn in the GC MS is a result of self chemical
ionization.125
The rhodium (II) perf luorobutyrate complex was observed to
exhibit greater activity than the rhodium trifluoroacetate complex
for the hydroformylation of 1-hexene. (35 turnovers for Rh2(pfb)4
versus 25 turnovers for Eh2(tfa)4 after 5 hours of reaction). In
both systems the isomer ratio (mol linear/ mol branched product) was
less than one. The increase in activity for the
perfluorocarboxylate ccnplexes is believed to be related to the

97
r
] *
Figure 3-2. A Sample Gas Chromatograph of the Products Formed
After the Hydroforrnylation of 1-Hexene with the
Rhodium(II) Perfluorocarboxylate Catalyst at 100°C.

Figure 3-3. A Sanple Mass Spectrum of the Solution After
Reaction with Enriched 13Carton Monoxide.
(A) 1-Hexene (B) Heptaldehyde.

100v:
45
I NT
30
T—
20
39
57
75
iilL
103
85
6
40
60
—r~
80
100
T r-
Tie
m/e
VO
VO
/I

100
increased ability of the Rh2 (pfb) 4 complexes to bind olefins when
compared to the Rh2(tfa)4. Doyle et al. reported that the Rh2(pfb)4
complexes will bind olefins three times better than the Rh2(tfa)4
complexes.89 These results appear to correlate with the observed
activity for the hydroformylation of 1-hexene.
Effect of Added Triphenvlphosrhine on Catalytic Activity and
Selectivity
The addition of triphenylphosphine to the rhodium
perfluorocarboxylate complexes was investigated and found to result
in an increase in activity for the hydroformylation of 1-hexene to
aldehyde products. The results of experiments where the ratio of
triphenylphosphine to rhodium (II) perfluorabutyrate was varied are
shown in Figure 3-4. As can be seen from the comparative activity
curves, the addition of FPh3 results in an increase in the activity
of these systems for the hydroformylation reaction. At low
phosphine to dimer ratios the formation of the hydrogenated olefin,
hexane, was detected by GC MS. At higher phosphine ratios the
hydrogenation reaction is suppressed and the primary reaction is
hydroformylation. In Figure 3-4, the levelling off of the activity
curves is a result of depletion of the reactant gases in the
pressure bottle apparatus. The reactors may be recharged with H2
and CD and the hydroformylation reaction is resumed.
The addition of triphenylphosphine not only results in an
increase in the activity of the catalyst system for hydroformylation
tut the selectivity of the system for the formation of the desired
linear product is also increased. These results are shown in the

TON
101
200.00 -
TIME (HOURS)
Figure 3-4. Activity Curves for the Formation of
Heptaldehyde with Varying Ratios of Rhodium (II)
Ferfluorobutyrate to Triphenylphosphine.
(A) 1:5 (B) 1:3 (C) 1:1.

102
series of bar graphs in Figure 3-5 where the isomer ratio (mol
linear /mol branched product) is plotted versus the ratio of dimer
to phosphine. Upon addition of PFh3, the increased formation of
heptaldehyde over 2-methyl hexanal is observed. At a dimer to
phosphine ratio of 1:1 the isomer ratio is 1.8 while at a phosphine
to dimer ratio of 1:5 the ratio is 4.6. At a ratio of 7:1
(PFh3:Kh2(pfb)4), 10% of the 1-hexene reactant has been converted to
aldehyde product after 5 hours of reaction.
Hydroformylation systems based upon rhodium usually employ
soluble rhodium carpi exes, such as RhH(OO) (PPh3) 3, and added
triphenylphosphine as the catalyst. The addition of excess
triphenylphosphine has been shown to result in a decrease in the
rate of hydroformylation while increasing the product
selectivity.115'116'126 When excess phosphine is present, the
decreased activity is proposed to result iron the difficulty in the
loss of FFh3 iron EhH(OO) (PPh3)3 during catalysis. The loss of
phosphine is proposed to open a vacant coordination site on the
rhodium center for binding of reactants as shewn in Equation 3-8.
EhH(GO) 2 (PFh3) 2 + olefin < > KhH(00)2(FFh3) olefin + PPh3
(3-8)
The addition of triphenylphosphine increases the formation of more
of the desired linear aldehyde product via a steric interaction.127
The presence of bulky phosphine ligands results in the formation of

Figure 3-5. Bar Graphs Illustrating the Effect of
Added Triphenylphosphine on Isaner Ratio.
MOLES LINEAR/BRANCHED ALDEHYDE
o —- r>o c -f*. c_n cd —i
103

104
a higher concentration of linear alkyl intermediates by suppressing
isomerization of the reactant olefin prior to addition across the
rhodium hydride bond. Added triphenylphosphine has also been shown
to minimize the formation of dimeric complexes such as
[Rh(00) (PFh3)2]2 which have been reported to be inactive for the
hydroformylation reaction.118
In the rhodium perfluorocarboxylate system studied in this work
the addition of triphenylphosphine was found to result in an
increase in both the catalytic activity and selectivity of the
system. The increased activity of the system is proposed to be due
to the presence of the perfluorocarboxylate groups in the
rhodium(II) carboxylate system. The electron-withdrawing ability of
the carboxylate ligands results in an increase in the lewis acidity
of the rhodium center enhancing the ability for coordination of the
reactants. These groups could also dissociate during catalysis
thereby opening up a coordination site on the rhodium center for the
binding of reactants such as the olefin. This alternative pathway
for coordination of the olefin would minimize a decrease in activity
upon addition of phosphine via the equilibria shewn in Equation 3-8.
Comparative Studies with Other Rhodium Carboxylate Complexes
Comparative studies were conducted for the hydroformylation of
1-hexene employing rhodium(II) carboxylate complexes in the presence
of 5 times molar ratio of added triphenylphosphine. The activity of
rhodium (II) trifluoroacetate in the presence of triphenylphosphine
was compared to rhodium (II) perfluorobutyrate as shewn in Figure

TON
105
TIME (HOURS)
Figure 3-6. Ccnparative Activity Curves for the Hydroformylation
of 1-Hexene with Rhodium(II) Perfluorobutyrate and
Rhodium(II) Trifluoroaoetate with Added Phosphine.
Rh2(pfb)4: (A) Linear, (D) Branched.
Rh2(tfa)4: (B) Linear, (C) Branched.

106
3-6. As shown in the figure, the rhodium perfluorobutyrate
phosphine system exhibits greater activity and selectivity than the
rhodium trifluoroacetate phosphine system. The increased activity
exhibited by the perfluorobutyrate system is suggested to be
related to the reported increase ability of the rhodium
perfluorobutyrate complexes to bind olefins better than the
trifluoroacetate corplexes.89 The perfluorobutyrate system also
exhibits increased product selectivity for the formation of the
linear aldehyde product. An isomer ratio of 4.6 was observed for
Rh2(pfb)4 versus 1.6 for Rh2(tfa)4). This is proposed to result
from steric effects in the system from presence of the larger
perfluorobutyrate ligand as compared to the trifluoroacetate ligand.
There has been a lot of controversy as to the exact mechanism
of rhodium catalyzed hydroformylations.102 >116 The activation of
dihydrogen by a rhodium acyl species and the formation of a rhodium
alkyl complex upon olefin coordination to a hydrido species have
both been preposed as the rate determining step. The observations
in this study would seem to correlate more closely with those by
Kastrup and ccworkers involving the coordination of olefin as the
rate determining step.
Two nonfluorinated rhodium carboxylate complexes were used for
comparison of activity for the hydroformylation of 1-hexene.
Rhodium(II) acetate and rhodium(II) butyrate were investigated in
the presence of five times excess triphenylphoshine under similar
reaction condition employed with the fluorinated

107
carboxylate complexes. The carboxylate complexes did exhibit
activity for the hydroformylation of 1-hexene to heptaldehyde
products. Within 5 hours of reaction, almost 200 TCN (turnover
numbers=mol product/mol catalyst) were observed though decomposition
of the rhodium complexes also occurred. This was evident from the
appearance of black precipitate and plating of metal in the reactor
vessel. The activity observed in these systems is suggested to be
associated with decomposition of the dimers. Unlike the alkyl
carboxylate complexes investigated, the reactions employing the
fluorinated carboxylate complexes remained homogeneous during the
hydroformylation reaction.
Comparative Studies with Rhodium(I) Complexes
The hydroformylation activity for the perfluorocarboxylate
complexes was compared with two commonly employed hydroformylation
catalysts. Chlorocarbonyl bis(tripherylphosphine)rhodium(I),
RhCl(OO) (PEh3)2, was investigated and found to be inactive for the
hydroformylation of 1-hexene under the reaction conditions employed
(100°C, 50 psig). These complexes have been reported to
hydroformylate olefins under reaction pressure conditions of 100
atm. hydrogen and carbon monoxide.108 The necessity for high
reaction pressures with this complex is believed to be due to the
difficulty in forming the active catalytic species, RhH(00)2(PPh3)2,
from the precursor chloro complex.
Tris (triphenylphosphine) rhodium(I) carbonyl hydride,
RhH(00) (FFh3)3, a catalyst typically employed under mild reaction

108
conditions, was investigated for the hydroforraylation of 1-hexene.
The activity of this complex was found to be similar to that
observed for the Fh2 (pfb) 4/PPh3 system with a 1:3 dimer to phosphine
ratio. After 5 hours of reaction 43 turnovers are observed for the
perfluorobutyrate system compared to 38 turnovers with the
RhH(OO) (FFh.3) 3 system. Seme catalyst decomposition was observed to
occur during hydroformylation with the rhodium hydrido complex.
The similarity in catalytic activity for these two systems
suggests the formation of similar catalytic species in solution. It
is possible that the rhodium perfluorocarboxylate complexes are only
catalyst precursors which are transformed into the similar catalytic
species observed in the EhH(OO) (PEh3) 3 system. In the rhodium
hydrido system the active catalytic species are proposed to be
RhH(OO)2(PEhs)2•To get a better understanding of the
transformations that occurred with the rhodium perfluorocarboxylate
catalyst during reaction with triphenylphosphine, synthesis gas and
1-hexene a spectroscopic study was undertaken.
Investigation of the Rhodium Perfluorocarboxylate
Trirhenvlrhosphine Catalyst System During Hydroformylation
During the reaction of 1-hexene with the rhodium
perfluorocarboxylate complexes in the presence of added
triphenylphosphine color changes of the reaction solution are
observed. Prior to addition of triphenylphosphine, the initial
solution containing the rhodium (II) carboxyl ate complex is green
(characteristic for rhodium(II) carboxylate complexes). Upon
addition of triphenylphosphine the green solution changes to red.

109
Rhodium (II) carboxylate complexes in the presence of phosphine
donors are known to be red. During the hydroformylation reaction
(within minutes after placing the reactor in a 100°C oil bath) a
yellow-orange solution is formed indicative of rhodium(I) complexes.
The yellow-orange solution is active for the hydroformylation of 1-
hexene to heptaldehyde. These color changes are summarized in
Figure 3-7. FT IR, 19F and 31P NMR and visible spectroscopy were
Kh2(02CRF)4 PFh3 H2,00 100°C
+ 1-hexene > red solution > yellow-orange
green solution 1-hexene
Figure 3-7. Color Changes Observed During Reaction.
used to investigate the nature of the rhodium species formed during
reaction.
The spectroscopic studies in this investigation were conducted
on active systems. During the hydroformylation reaction, samples
were withdrawn from the reactor and investigated spectroscopically.
These studies were not conducted in situ.
The 31P NMR spectrum of the rhodium perfluorobutyrate-
triphenylphosphine species during hydroformylation is shown in
Figure 3-8 and the 31P chemical shifts are listed in Table 3-1. The
spectrum contains two main sets of doublets. No free
triphenylphosphine was detected. A similar spectrum was obtained
for the rhodium(II) trifluoroacetate triphenylphosphine system.
This type of splitting pattern is characteristic of mononuclear bis¬
and tris (triphenylphosphine) rhodium complexes and not of phosphine

Figure 3-8.
31P NMR Spectrum of the Reaction Mixture During
Hydroformylation with Wi2(°20C3F7)4 and 5PEh3.

Ill
O PPM

112
Table 3-1. 31P NMR Data for Rhodium Perfluorocarboxylate
Carpi exes.
Complex
Coupling
31P Chemical Shift3 Constant(Hz) Solvent
Rh2(020C3F7)4
+ 5PFh3 during
hydroformylation
30.81 d
48.95 d
131.3
180.0
c6d6
Rh2(02CCF3)4(PEh3)2b
32.8 d
-24.2 d
-15.1
166.0
92.7
CDC1;
Rh(02CCF3)(PEh3)3c
34.19 d of d
52.34 d of t
148.1
184.3
CDC1:
M1(02CCF3)aO(PEh3)2
31.76 d
131.8
CDC1
Rh(02CCF3)(PFh3)3
during hydroformylation
32.13 d
130.3
c6d6
Rh(O2CCF3)C0(PFh3)2
during hydroformylation
32.63 d
133.1
c6d6
a All chemical shift are with respect to external 85% H3F04
b Telser, J.; Draqo, R.S. Inorq. Chem, 1884,23,2604.
c same spectra obtained for preparation frcm Ki2(°2CCF3)4 with
XS PFh3 and frcm reaction of HRh(PEh3)4 with CF3OOOH
JpiP2= 40.8Hz; (^doublet, t=triplet

Figure 3-9. 19F NMR Spectrum of the Reaction Mixture During
Hydroformylatian with Fh(020C3F7)4 and 5PFh3.

114

115
Table 3-2. 19F NMR Data for Rhodium
Perfluorocarboxylate Complexes.
Complex
19F Chemical Shift3
Solvent
Rh2(02CC3F7)4
-81.03, -117.59, -127.24
c6d6
Rh2 (02CC3F7) 4 + 5FEh?
during hydroformylation
-81.1, -116.8, -119.5,
-126.9, -127.2
c6d6
Ki2(02CCF3)4
-75.04
toluene d.
Rh(020CF3) (PEh3)3b
-74.70, -74.79, -75.08
-75.57
CDCI3
Rh(020CF3) (Pñl3)3
during hydroformylation
-75.6
CDCI3
Rh(02CCF3)00(PHl3)2
-75.37
CDCI3
Rh2(02CCF3)4(PEh3)2c
-74.4, -74.75, -75.88
CDCI3
a All chemical shifts are with respect to internal CPCI3 and were
obtained at 27°C unless otherwise stated.
b Same spectra for preparation from reaction of Rh2(02CCF3)4 with
XS PEh3 and from reaction of HRh(PPh3)4 with CF3CDCH.
c Telser, J.; Drago, R.S. Inora. Chem.. (1984), 23, 2604.

Figure 3-10. Infrared Spectrum of the Reaction Mixture After
Hydroformylation with Rh(020C3F7)4 and 5PPh3.

WAVENUMBERS (CM-l)
117

118
Table 3-3. Infrared Data for Rhodium
Perfluorocarboxylate Ccnplexes
Ccnpcund V as(00)2 can-1 (Nujol mull)
Rh2(02C3C3F7)4
Rh2(02CX3’3)4
Kl2(020CF3)4(PHi3)2b
Rh(020CF3) (PEÍ13)3c
Rh(020CF3) (FBl3)3d
Rh(02CrF3) ^1(020CF3) (PFh3)3 + 3FHl3
during hydroformylation
Rh2(020C3F7)4 + 5PFh?
during hydroformylation
1665
1650
1715w, 1654m, 1652m
1671
1670
1689
1671W, 1658m, 1643m
1715
a s=strong, m=medium, w^weak
b Telser, J.; Drago, R.S. Inora. Chem. (1984), 23, 2599.
c prepared from reaction of Ki2(020CF3)4 with XS PPh3.
d prepared iron rection of HRh(FEfc3)4 with CF3GOOH.

119
adducts of rhodium(II) carboxylate complexes. Previous studies by
Tel ser and Drago were conducted on the Rh^C^CCT^J^PPf^^
system.128 The 31P chemical shifts for the bis phosphine adduct are
listed in Table 3-1. Comparison of the chemical shifts of
Rh2(02CCF3)4(P^13)2 with those of the species formed in this work
during hydroformylation suggest that a dimeric complex is not the
major species present in solution during reaction.
Further evidence for this is provided by the 19F NMR spectrum
shewn in Figure 3-9 and the 19F chemical shifts listed in Table 3-2.
Comparison with the 19F chemical shifts with the rhodium (II)
perfluorobutyrate complex (see Table 3-2) containing a bidentate
carboxylate group suggest the presence of carboxylate ligands which
are monodentate. The infrared spectrum of the rhodium carboxylate-
phosphine complex during hydroformylation shewn in Figure 3-10 (and
the asfex^) band is listed in Table 3-3) support the presence of
monodentate carboxylate ligands.
Based upon these spectroscopic findings it is proposed that the
rhodium (II) perfluorocarboxylate complexes in the presence of
triphenylphosphine are transformed into mononuclear rhodium
perfluorocarboxylate triphenylphosphine complexes which are active
catalysts for hydroformylation. In order to get a better
understanding of the reactions of the dimer with 1-hexene and
triphenylphosphine a visible study was undertaken.

120
Visible Investigation on the Effect of Added Olefin and Phosphine to
the Rhodium (ID Ferfluordbutrvate Complex
The visible spectral changes accompanying sequential addition
of 1-hexene to Rh2(pfb)4 (4.2E-4 M) in anhydrous dichlorcmethane at
619 nm which includes free Eh2(pfb)4 is shewn in Figure 3-11.
During the addition of 1-hexene the solutions remained green
suggesting the presence of an intact rhodium dimer. A visible
spectrum obtained for the dimer in 100 fold excess of olefin
exhibited similar absorptions. An equilibrium constant of 7OK-1 was
calculated for the 1:1 complex formation between the dimer and the
olefin (see Equation 3-9) at 70% saturation. A study conducted by
Doyle reported an apparent equilibrium constant of 150M-1.87
^eq
Rh2(pfb)4 + olefin < > Eh2 (pfb) 4-olefin (3-9)
Rhodium (II) carboxylate dimers contain vacant sites available
for coordination with donor ligands.83 Adduct formation with donor
molecules would be expected to involve a two step process whereby
the 1:1 and then the 2:1 (donor:dimer) complexes would be formed.
Studies by Drago et al. have shewn that once the 1:1 adduct is
formed the second axial ligand is less strongly bound to the rhodium
at the second coordination site.84 The formation of a 1:1 adduct
between the rhodium dimer and 1-hexene is consistent with these
results.
The sequential addition of triphenylphosphine to a solution
ccntaining the rhodium(II) perfluorobutyrate complex resulted in
significant changes in the visible spectrum as shown in Figure

ABSORBANCE
121
WAVENUMBERS (run)
Figure 3-11. Visible Spectral Overlay Upon Sequential
Addition of 1-Hexene to Rhodium (II)
Perfluorobutyrate.

122
3-12. A decrease in the intensity of the absorption bands
attributable to the rhodium dimer and the appearance of an intense
absorption at 360 rim was observed. Upon addition of
triphenylphosphine to the initial green solution the solution
changes to red and then to yellcw. These changes are preposed to be
attributed to the cleavage of the rhodium dimer to produce
mononuclear rhodium ccnplexes. In order to get a better
understanding of the resulting ccnplexes formed upon addition of
triphenylphosphine to the rhodium perfluorocarboxylate ccnplexes and
their role in the catalytic hydroformylations further studies were
conducted.
Investigation of Species formed upon Reaction of Rhodium(II)
Perfluorocarboxylate Complexes with Triphenylphosphine
In this study, the objectives were to isolate and characterize
the ccnplexes formed upon addition of triphenylphosphine to the
rhodium(II) carboxylate dimers. The investigation of these
ccnplexes as catalysts for the hydroformylation of 1-hexene should
aid in a better understanding of the catalytic system formed upon
addition of phosphine to the rhodium dimers as previously discussed.
Preliminary studies of the reaction of excess triphenylphosphine
with Ki2(°2OCF3)4 were undertaken by Telser and Drago.121 Reaction
of excess PEh3 with the rhodium(II) trifluoroaoetate dimer was
reported to result in the cleavage of the Rh(II) dimer to produce
RhfC^CCT^) (PFh3) 3 and a yellcw oenpound best formulated as
Rh(0CCF3)3(FFh3)2 as shewn in Equation 3-10. The detailed

123
1 1
350 400 600 750
Figure 3-12. Visible Spectral Overlay Upon Sequential
Addition of Triphenylphosphine to
Rhodium (II) Perfluorobutyrate.

124
XS Pñl3 Rh(02CCF3)(PRl3)3 (ppt.)
Rh2(020CF3)4 > + (3-10)
Rh(020CF3)3(PEtl3)2
investigation of these complexes was beyond the scope of the
previous study.122 The preparation, continued characterization and
subsequent catalytic investigation of these rhodium carboxylate
phosphine complexes is warranted in this study.
The rhodium (II) perfluorobutyrate dimer was initially reacted
with excess triphenylphosphine for the isolation of complexes
similar to those shown in Equation 3-10. Unfortunately the reaction
of FFh3 with Rh2 (pfb) 4 yielded an intractable red oil from which a
pure solid could be isolated. In the catalytic hydroformylation
studies discussed above the addition of triphenylphosphine to
rhodium (II) trifluoroaoetate was shewn to result in the formation of
an active hydroformylation system. Characterization and catalytic
investigation of the resulting rhodium(I) complex formed in Equation
3-10 was undertaken.
Upon reaction of excess triphenylphosphine to the rhodium (II)
trifluoroaoetate complex the formation of an orange solid was
observed similar to that previously reported.121 Characterization
of this orange rhodium complex was conducted by using FT IR and FT
NMR. The infrared spectrum of the complex shown in Figure 3-13
contains an asymmetric carboxylate absorbance at 1670 cm-1 and is

125
listed in Table 3-3. The position of the band is in good agreement
with that reported by Tel ser and Drago121'122 and Dobson et al.124
Dobson et al. reported the preparation of Rh(02CCF3)(PFh3)3
from reaction of mononuclear rhodium (I) complexes with organic
acids and not from the reaction of rhodium (II) trifluoroacetate with
excess triphenylphosphine.124 This alternative preparation was
repeated and the resulting orange ccnplex was shewn to exhibit the
same characterization as Rh^OCf^) (PFh3)3 prepared from the dimer.
These results provide further evidence for the formation of the same
ccnplex frena different synthetic routes. A crystal structure has
not been reported for this complex though based on spectroscopic
evidence it is proposed to contain a monodentate carboxylate ligand.
The as(0C>2) stretches for the bidentate carboxylate group in
Rh2(C>20CF3)4 is at lewer wavenumbers (1665 cm-1) than the proposed
monodentate CF3002” group (1671 cm-1) in Rh(02 supporting monodentate coordination of the ligand. Further
characterization of this complex other than infrared, elemental, and
molecular weight data has not been reported.
Trifluoroacetate tris(triphenylphosphine) rhodium(I) would be
expected to exhibit a single 19F chemical shift attributable to the
monodentate CF3002“ group. This is not the case as indicated by the
19F spectrum as shown in Figure 3-14 and the 19F chemical shifts
listed in Table 3-2 for Rh(02GCF3) (PFh3)3. Assignment of these
peaks is difficult; presumably, they correspond to mono- and
bidentate CF3C302“ groups. Previous 19F NMR studies conducted by
Drago and Telser121 resulted in a complex spectrum for

Figure 3-13. Infrared Spectrum of Hhí^OCFj) (PIÍI3)

4064 I 3357 2 2650 3 2071 7 1718 2 1364 7 1011 2 828 89 652 15 475 41
1WAVFNUMBFRS (CM-1)
127

Figure 3-14. 19F NMR Spectrum of Rh(020CF3) (PFh3)3-

129

130
Rh2(C^CCF^4(PFh3)2 as well. For a series of MÍC^OR^GOÍPRvj^
complexes where (M=Ru, Os) rapid intramolecular exchange of the
mono- and bidentate carboxylate ligands was reported resulting in
complex 19F NMR spectra.129'130 It is possible that similar
equilibria occur with the RhiC^CCF^) (PFh3)3 complexes in this study.
The 31P NMR plectrum of Rh(C>20CF3(PFh3)3 is shewn in Figure 3-
15 and the 31P chemical shifts are listed in Table 3-1. A splitting
pattern characteristic for tris (triphenylphosphine) rhodium(I)
complexes is observed. Tris(triphenylphosphine) rhodium(I) chloride
exhibits similar splitting patterns and coupling constants (31PS =
32.2ppm, J= 146 Hz; 31PS = 48.9ppro, J= 192 Hz).131'132 Not shown in
Figure 3-14 but present in the spectrum is a peak at -4.5 ppm
corresponding to free triphenylphosphine. The presence of free PPh3
would suggest that a dissociative equilibria exists in solution as
shewn in Equation 3-11. It is suggested that the resulting
2Rh(C>20CF3) (PFh3)3 < > 2Eh(02CCF3) (PFh3)2 + 2PFh3
< > [Rh(02CXT3)(PEh3)2]2 + 2FFh3 (3-11)
complex after dissociation may be a dinuclear rhodium species rather
than a three coordinate species. lew temperature NMR studies did
not result in ary spectral changes. Further studies on this complex
should be conducted to confirm this proposal.
Spectroscopic studies have been conducted on the dissociation
of triphenylphosphine from tris (triphenylphosphine) rhodium(I)
chloride114 and tris (triphenylphosphine) rhodium(I) carbonyl
hydride116 by 31P NMR. In both studies, the presence of a

*e(Ema) 30 ranxpeds HWN dxe *ST-e amfcTj

132
34 PPM

133
bis (triphenylphosphine) rtiodium (I) species was not detected
spectroscopically but was postulated from kinetic results. It is
proposed that similar phosphine dissociation equilibria are
occurring in the tris (triphenylphosphine) rhodium(I) trifluoroacetate
system.
Studies were undertaken for the preparation of
perfluorobutyratetris(triphenylphosphine) rhodium(I),
Rh^FyOC^) (PFh3)3, from an analogous manner used in the synthesis
of the trifluoroacetate complexes, unfortunately upon reaction of
heptafluorabutyric acid with HRh(PEh3)4 an intractable oil was
obtained frcm which a pure solid could not be obtained. Other
synthetic routes were also investigated including the reaction of
silver and sodium perfluorobutyrate with Rhei(PFh3)3 and the
reaction of heptafluorabutyric acid with Rh(02CCH3) (FFh3)3. In each
case a pure solid could be obtained. The application of these other
synthetic routes for the formation of Rh(C>2CCF3) (FEh3)3 also
resulted in an intractable oil from which a pure solid could not be
obtained.
Investigation of RhfOnCCF^ (FEh3^3 for catalytic Hvdrofonnvlation of
1-Hexene
Trifluoroacetate tris (triphenylphosphine) rhodium (I),
Eh(C>20CF3) (Pfh3)3, was investigated for catalytic activity for the
hydroformylation of 1-hexene to heptaldehyde and 2-methyl hexanal.
The ccnplex was found to produce 50 turnovers after 5 hours of
reaction and exhibit an isomer ratio of 1.8 which is similar to the
activity of the rhodium (II) trifluoroacetate system with comparable

134
rhodium to PÍÍI3 ratios. The addition of triphenylphosphine to the
Mi(020CF3) (PEÍ13)3 system resulted in an increase in catalytic
activity and product selectivity of the system as shewn in Table 3-
4. As shown in the table, 225 turnover numbers and an isomer ratio
of 4.3 was obtained for the Rh(020CF3) (PEti3)3 system in the presence
of 5 times molar excess of FB13. The formation of hexane (10%) was
also detected by GC MS. Trace amounts of alcohol were detected only
after long reaction times.
Investigation of the Khi02CCF3) fPFh3)3 System Curing Reaction
During the catalytic hydroformylation of 1-hexene, the
Fh(C>20CF3) (PEh3) 3 system was investigated by infrared spectroscopy
and 19F and 31P NMR. The infrared spectrum obtained during
hydroformylation with Rh(0C>20CF3) (PEh3) 3 and 3PFh3 is shown in
Figure 3-15. Similar spectra were obtained either in the absence of
added PFh3 or with 5PFh3 added. The absorptions between 2000 and
2100 cm-1 are attributed to the presence of a carbonyl complex. The
strong 1723 cm-1 peak is attributed to the aldehyde product. The
as (CD2) region exhibits three peaks (listed in Table 3-3 for
comparison with other infrared data) at 1671, 1658 and 1643 cm-1.
The Rh(020CF3) (PEh3)3 complex prior to hydroformylation exhibited a
strong 1671 cm”1 peak which is only weakly observed in Figure 3-15.
The presence of triphenylphosphine oxide was also observed in the
infrared spectrum as indicated by a strong P=0 absorbance at 1195
cm-1. The formation of 0=PPh3 is ccmonly encountered in
hydroformylation reactions in which triphenylphosphine is present

135
Table 3-4. Camparison of 1- Hexene Hydroformylation
Activity for Various Rhodium(I) Catalysts
Catalyst
TON3
Iscmer Ratio
Rh(tfa) (PEti3) 3
51
1.8
Rh(tfa) (FRi3) 3
70
3.2
+ 3PFh3
Rh(tfa) (FE*i3)3
225
4.3
+ 5PEfc3
Rh(tfa)00(PFh3)2
40
1.8
RhH(CO) (PFh3)3
38
2.7
RhH(CO) (PEh3)3
100
4.3
+ 5PFh3
a all reactions conducted at 50psig H2/CO (1:1) and
lOO^C, Turnovers (TON) calculated after 5 hours of
reaction, tfa=(C>2CCF3).

136
and has been reported to lead to deactivation of the catalyst.100
The presence of a rhodium hydride peak was not observed in the 1H
NMR.
Further characterization of the trifluoroaoetate
tris (triphenylphoshine) rhodium(I) system during hydrofonnylation
was provided by 19F and 31P NMR data. The 31P NMR spectrum was
found to contain a doublet at 32.13 ppm with a coupling constant of
130.3 Hz and a large peak at 29.5 ppm attributed to
triphenylphosphine oxide as shewn in Figure 3-16. No free
triphenylphosphine was observed in the 31P NMR. The observed
doublet is indicative of bis (triphenylphosphine) rhodium(I)
complexes. Trifluoroaoetate carbonyl bis (triphenylphosphine)
rhodium (I), RhiC^CCT^OOiPFl^^, has been reported to exhibit a 31P
spectrum containing a doublet at 32.9 ppm and a coupling constant of
130.8 Hz.133
The 19F NMR spectrum of the solution during the reaction was
found to contain a single 19F resonance at -75.6 ppm as listed in
Table 3-2. Based upen the spectroscopic data obtained for the
Rh(020CF3) (PFh3)3 system during hydrofonnylation it is proposed that
the catalytic species formed in solution is a
bis (triphenylphosphine) rhodium trifluoroaoetate carbonyl species,
Rh(C>20CF3) (00)x(PEh3)2* To get a better understanding of the
species formed in the system during hydrofonnylation,
Rh(02CCF3)00(PEh3)2 was prepared and investigated.

Figura 3-16. Infrared Spectrum of the Reaction Mixture Daring
Hydroformylation of 1-Hexene with Rh(020CF3) (PFh3)3.

WAVENUMBERS (CM-l)
138

139
Investigation of Trifluoroacetate Carbonyl Bis(triphenylphosphine)
Rhodium(I)
Trifluoroacetate carbonyl bis(triphenylphosphine) rhodium(I)
was prepared as described in the experimental section. 124 The
infrared characterization of this yellcw complex shews the presence
of a carbonyl band at 1980 cm-1 and an asymmetric carboxylate band
at 1689 an”1 as listed in Table 3-3. A single 19F NMR resonance at
-75.4 (see Table 3-2) was found. The 31P NMR spectrum exhibited a
doublet at 31.76 ppm with a coupling constant of 132 Hz. This NMR
data supports the formation of a similar complex in the
Rh(02OCT'3) (PFh3)3 system during hydroformylation as previously
described.
The activity of Rh(02CCF3)00(PFh3)2 for the hydroformylation of
1-hexene was investigated. After 5 hours of reaction 40 turnovers
were observed with an isomer ratio of 1.8 as shewn in Table 3-4.
Comparison with the hydroformylation results for Rh(02CCF3) (PFh3)3
shew similar isomer ratios yet the triphenylphosphine complex
exhibited greater activity (50 TON).
The Ki(02C!CF3)CX)(PEh3)2 system was investigated during
hydroformylation by 31P NMR. The 31P NMR spectrum (shown in Figure
3-17) exhibited a doublet at 32.6ppm (J= 133Hz) listed in Table 3-1.
The spectrum is similar that obtained for this complex before
reaction and to RhiC^CX^) (PFh3) 3 during reaction ( see Table 3-1).
These results suggest the formation of similar reactive species.

140
Comparative Hydroformylation Studies with Hvdrido Carbonyl
Tris(triphenvlphosphine) Rhodium(I). RhHfOO) (PPh3)3
Studies were conducted to compare the activity of
Rh(020CF3)(PEh3)3 with RhH(OO)(PEh3)3. The activity for the for the
hydroformylation of 1-hexene with Rh(C>20CF3) (PFh3)3 versus
RhH(OO) (PEh3)3 is shewn in the bar graph in Figure 3-17. The
catalysts were compared both in the absence of excess
triphenylphoshine and in the presence of 5 times molar excess
triphenylphosphine. The total turnover numbers for the aldehyde
products and the iscmer ratios are listed in Table 3-4. The rhodium
trifluoroaoetate complex was found to exhibit greater activity for
the hydroformylation of 1-hexene than the rhodium hydrido complex.
These results are more pronounced for the reaction conducted with
excess triphenylphosphine where 225 turnovers are observed for the
trifluoroaoetate complexes versus 100 turnovers observed for the
hydrido complex. For both complexes with added PFh3 an isomer ratio
of 4.3 was observed.
The increased activity observed in the Kh(02CCF3) (PFh3)3 system
is attributed to the presence of the electron withdrawing
trifluoroaoetate ligand which should enhance the Lewis acidity of
the rhodium center. This would be expected to increase the ability
of the complex to coordinate and activate the reactants. The
addition of excess tripheny lphosphine to the rhodium hydrido system
would drive the equilibrium in Equation 3-12 to the left. This
should hinder the formation of RhH(00)2(FEh3) olefin upon loss of

Figure 3-17.
31P NMR Spectrum of the Rection Mixture During
Hydroformylation of 1-Hexene with Fh(02CCF3) (PPh3)3.


TURNOVER NUMBERS AFTER 5 HOURS
143
250
CATALYST
Figure 3-18. Bar Graph Comparison of the Hydroformylation
Activity of Rh(C»2CCF3) (PEh3)3 Versus RhH(OO) (PFh3)3.

RhH(OO) 2 (Píh3) 2 + olefin <
144
> RhH(00)2(PEh3) (olefin) + PPh3
(3-12)
PFh3 frcm RhH(00)2(FFh3)2. In the rhodium trifluoroacetate system a
similar dissociative reaction would be expected to occur as shown in
Equation 3-13. The weakly coordinating trifluoroacetate group could
cilso dissociate to form an ion pair and open a coordination site on
the rhodium center. This would provide an alternative route for the
2Kl(020CF3) (PFh3)3 <—> 2Rh(020CF3) (PEh3)2 + 2PEh3 (3-13)
catalytic cycle to continue. Further discussion of an alternative
route for catalysis in the mechanism for hydroformylation with the
rhodium trifluoroacetate-phosphine system is discussed in a later
section.
During the hydroformylation of 1-hexene employing
KhH(OO) (PPh3)3, decomposition of the catalyst was observed. The
initial yellow solution changed to brown and a precipitate formed in
the reactor. These results are encouraging in view of the high
activity reported for RhH(OO) (FFh3)3 as a hydroformylation catalyst.
It is cilso proposed that this trifluoroacetate complex may be
present as a cationic complex possibly, [Rh(FFh3)3]+[ (020CF3) ]"
which results in the facile availability of vacant coordination
sites for activation of the reactants. If a cationic rhodium
complex is present it should be possible to ionicly exchange the
complex onto a polymeric exchange resin and develop a heterogeneous
hydroformylation catalyst.

145
A heterogeneous system based upon rhodium would be industrially
attractive. This would alleviate separation problems encountered
when olefins are hydroformylated which have a lcwer boiling point
than their corresponding aldehyde product (as with 1-hexene) while
allowing milder reaction conditions and high activity to be achieved
by employing rhodium catalysts. Typically, rhodium catalysts are
heterogenized via ligand exchange onto phosphinated inorganic oxide
or polymer supports134 as shewn in Equation 3-14. The use of
covalently anchored catalysts often results in the loss of the
expensive rhodium catalyst due to leaching under reaction
conditions.135 The ability to strongly bind a homogeneous
hydroformylation catalyst to a support (possibly via an
electrostatic interaction) would be expected to result in the
support-PFh2 + KiIx(PEh3)y <—> support-PEh2)zEhIic(PFh3)y_2
+ yPEh3 (3-14)
formation of an active heterogenized hydroformylation catalyst. The
preparation of sulfonated linear polystyrene (PSSA) to form PSSA-
Rh(III) film as potential catalyst materials for reaction with H2
and <30 has been previously reported.136
Preparation of rRh(PFh3)3l~r(O2CCF3) ]- Exchanged onto Nafion
Preliminary studies were undertaken to heterogenize the rhodium
trifluoroacetate catalyst. The resin used for exchange of
Eh(PEh3) + (02CCF3)” was Nafion. The use of this fluorocarbon support
may help to solubilize the Rh(Pfh3) 3+(02CCF3)- complex in the

146
hydrophobic polymer matrix and allow for exchange interaction
between the trifluoroacetate group and the hydrophilic sulfonate
group of the polymer. Both the hydrogen and sodium form of Nafion
were investigated with the aim being to exchange [Rh(PFh3) 3]+
cation for the proton or sodium cation of the sulfonate groups of
the support as shewn in Equation 3-15.
F F F F F
i i i i i
F F 0 F F
[Rh(PEh3)3]+[tfa]'
Tf
SC^H
F F F F F
mi 11_
mi ii
F F 0 F F
I
'f
S03[Kh(PFh3)3]+
(3-15)
The resulting resin is yellcw indicating the presence of the
rhodium(I) complex though it is unclear whether the complex has been
actually exchanged onto the resin or is trapped in the polymer
network. The formation of the ionicly exchanged complex would be
expected to be equilibrium driven as shewn in Equation 3-16.
P-SC^H + [Eh(PEh3)3]+[(02C3CF3)]- < > P-SC^-RhiPPtVj) 3+ +
CF3OOOH (3-16)
To drive the equilibria to the right the trifluoroacetic acid
would need to be removed during heterogenation as shown in Equation
3-16. lew loadings of rhodium catalyst (10-5 mole/g Nafion) were
used in preparation of the supported complex with an unknown amount
of acid being removed during preparation. Other studies have shown

147
that rhodium(I) complexes have a preference for CF3C3D2- over CF3SO3-
in metathesis reactions.137 It has also been postulated that Nafion
may be represented as an inverted micelle.138 This would be
expected to cause an increase in difficulty of the exchange shown in
Equation 3-16.
Hvdrofonnvlation of 1-Hexene using the Polymer Supported Rhodium
Catalyst
The rhodium complex supported on Nafion was investigated for
catalytic activity for the hydroformylation of 1-hexene. The
supported complex on Nafion-H was initially investigated. Upon
reaction of H2, 00 and 1-hexene with the supported rhodium catalyst
no products indicative of hydroformylation were detected after 24
hours of reaction. The formation of a long chain hydrocarbon was
detected by GC MS. This product is proposed to be a result of
polymerization of 1-hexene due to the presence of the strong acid
nature of remaining -SO3H groups of the support. The use of Nafion
as a strong acid catalyst has been previously reported. 139 To
decrease the acidity of the material and presumably its
polymerization ability Rh-nafion was reacted with a sodium carbonate
solution. This reaction should exchange ary remaining protons with
sodium ions and result in the formation of materials which would be
expected to exhibit activity for the hydroformylation of 1-hexene.
Upon reaction of the Na2OC>3 treated Rh-Nafion with H2, 00 and
1-hexene the catalytic formation of aldehyde products was detected.
After 10 hours of reaction 17 turnovers were calculated with an
isctner ratio of 0.8. The initial yellcw resin was also observed to

148
change to brown-black during the hydroformylation reaction. The
selectivity and activity of this system is lower than its
homogeneous analog where 50 turnovers and an isomer ratio of 1.8 was
observed with Kh^OCT^) (PFh3)3.
The addition of triphenylphosphine to the supported rhodium
system was also investigated. Five times excess of PPh3 was added
similar to the homogeneous trifluoroacetate system. After 8 hours
of reaction 88 turnovers were calculated with an isomer ratio of
4.0. The resulting black resin was removed from the reactor and
washed with benzene, water and hexanes and then placed back into
the reactor and allowed to react with H2, 00 and 1-hexene in the
presence of added triphenylphosphine. After 8-10 hours of reaction
the resin was still found to exhibit activity for the
hydroformylation of 1-hexene to aldehyde products. This procedure
was repeated with no observed loss in hydroformylation activity.
A comparison of the hydroformylation results for the
homogeneous and heterogenized Rh(020CF3) (FFh3)3 systems are shown in
the bar graph in Figure 3-19. In the graph, bar A is representative
of the homogeneous system and bars B-D represent the heterogenized
system after successive washing and repeated reaction with H2, 00
and 1-hexene. In both systems an isomer ratio between 4-5 was
observed.

MOLES OF TOTAL HEPTALDEHYDE
149
250
A B C D
RHODIUM PPh3 (1:5)
Figure 3-19. Bar Graph Comparison of the Homogeneous Versus the
Heterogeneous Hydroformylation System.
(A) Homogeneous, (B-D) Heterogeneous.

150
Leaching of the Catalyst from the Resin is Evident
In an attempt to investigate if loss of the rhodium complex
from the support during catalysis had occurred, experiments were
conducted on the solutions after hydroformylation with Nafion
supported rhodium complex. Successive solutions were investigated
for hydroformylation activity after a run with the heterogeneous
system. In all cases the solutions exhibited activity for the
hydroformylation of 1-hexene. Hie exact calculation of turnovers is
difficult since the amount of leached rhodium complex was not
determined. Removal of the liquid by vacuum of the solution
resulted in the appearance of a white solid identified as
triphenylphosphine oxide by infrared spectroscopy. No bands in the
carbonyl region were found to support the presence of a rhodium
carbonyl complex. Attempts to eliminate leaching of the rhodium
catalyst from the support by varying the method of preparation were
unsuccessful. Other supports should be investigated for
heterogenizing the rhodium trifluoroacetate complex with the aim
being to eliminate leaching during catalysis.
Hydroformylation of Propylene Using Tris (triohenvlphosphine)
Rhodium f I) Trifluoroacetate Incorporated in a Polymer Membrane Film
Preliminary experiments were conducted to probe the activity of
Rh(02CCF3) (FB13) 3 encapsulated in a polymeric membrane film for the
hydroformylation of propylene. This type of solid-gas reaction
should eliminate the problem of catalyst leaching encountered in the
solid-liquid reaction previously discussed. The reactor setup was
identical to that employed by other group members.140 The reactor

151
contains the catalyst in a polymeric membrane film which is
maintained between two chambers. The entire apparatus is evacuated
and the upper chamber is filled with H2, 00 and propylene (1:1:1).
The reactant gases are allowed to diffuse through the polymer and
react with the catalyst to yield the products.
The rhodium trifluoroacetate catalyst with five times excess
PEh3 was encapsulated into a polybutylmethacrylate membrane film.
Reaction conditions of 2 atmospheres pressure and 100°C were
employed. Propylene was observed to be hydroformylated to
butyraldehyde. No branched aldehyde product was detected by gas
chromatography. After 48 hours of reaction, 8.1X10-7 moles of
butyraldehyde were produced. While these results are preliminary,
the high selectivity observed for the linear aldehyde product under
mild reaction conditions warrants further investigation of this
system.
Hvdroformvlation of Other Olefins with KhfChOCT^) (FFhj^
Other olefins were investigated to probe the reactivity of the
rhodium trifluoroacetate-triphenylphosphine system for catalytic
hydroformylation. Styrene was found to be readily hydroformylated.
The formation of benzene propanal was conformed by GC MS as shown in
Figure 3-20. For comparison the reactant styrene is included in the
figure. Ethyl benzene was also identified by GC MS. After
hydroformylation of styrene the presence of a viscous liquid was
also present in the reactor. This is proposed to be polystyrene
formed thermally during the hydroformylation reaction. Ethyl vinyl

Figure 3-20. A Sauple Mass Spectra of the Reaction Solution After
Hydrof ormylation of Styrene.
(A) Styrene, (B) Benzene Propanal.

1 00/
I NT
51
39
30
63
105
77
91
■ I,» ■ I |
80 100
134
20
40
60
120
"i—^ 1—
140
100 X
INT
51
3? r v .
38
T“
20
L-r
104
78
63
1 J.
40
r
60
n~
80
—r~
ios
->—i—
120
r b
rn/e
r A
m/e
153

154
ether was also investigated as a substrate for hydroformylation and
found to be hydroformylated to the aldehyde, 3-ethoxy propanal. The
formation of 3-ethoxy propanal was confirmed by GC MS as shewn in
Figure 3-21. Other unidentifiable products were also formed during
hydroformylation of ethyl vinyl ether. In both of the reactions
described above the formation of other aldehyde product isomers is
proposed though separate iderrtification by GC MS was not attempted.
Hydrogenation of 1-Hexene and other Miscellaneous Reactions of 00.
H2 and Heptaldehvde with RhfCbCCFj) (PFt^ 3
The hydrogenation of 1-hexene was also investigated with the
Eti^OCT^) (PEÍI3) 3 catalyst. Loss of the reactant hydrogen occured
upon reaction of 1-hexene with H2. The formation of hexane was
confirmed by GC FITR. The hydrogenation of olefins with
Rh^CXJ^) (PFh3)3 has been previously reported.98 The hydrogenation
activity of Rh^CCT^) (PEh3)3 was found to be lewer than the
activity observed with Wilkinson's hydrogenation catalyst,
RhCl(FFh3)3.
The reactivity of Rh(02CCF3) (PEh3) 3 with carbon monoxide,
hydrogen and heptaldehyde was also investigated by infrared
spectroscopy. Upon bubbling carton monoxide through a suspension of
Rh(C>2CCF3) (PFh3) 3 in benzene at 25°C and 1 atm. the formation of a
bright yellcw solution was readily observed. Infrared
characterization of the solution shewed a band at 1980 cm-1 assigned
to a carbonyl stretch and a band at 1689 cm-1 assigned to the
asymmetric carboxylate stretch. These assignments are identical to
those previously obtained for Rh^CCT^OOiPR^^. A strong

Figure
i_2i. a Saxiple Mass Spectra of the Reaction Solution After
Hydroformylation of Ethyl Vinyl Ether.
(A) Ethyl Vinyl Ether (B) 3-Ethoxy Propanal

156

157
absorbance at 360nm was also observed in the UV region. These
results suggest the formation of a bis(phosphine) carbonyl complex
upen reaction of Rh(02CCF3) (FFh3) 3 with carbon monoxide as shown in
Equation 3-17. Upen sweeping the solution with nitrogen or hydrogen
the solution color and infrared remained unchanged indicating that
the loss of 00 from the bis (triphenylphosphine) complex is not
facile.
Kl(020CF3) (PFh3) 3 + 00 < > Rh(02CCF3)aO(PI:h3)2 + PPh3
(3-17)
These results may be extrapolated to the observed
hydrofonnylation activity of Eh(020CF3)00(FFh3)2 which was lower
than the activity observed with Kh(02CCF3) (PEh3)3. It is possible
that during catalysis the reactivity of 00 from the carbonyl complex
is slower than the tris (triphenylphosphine) complex when either of
these is employed as the immediate precursor. The formation of the
acyl complex would then be expected to be slower with the
Kh(02CCF3)00(PFh3)2 precursor and hence the eventual formation of
aldehyde product.
An orange suspension of Eh(C>20CF3) (FFh3)3 in benzene was also
reacted with H2 at 25°C and 1 atm. After 1 hour the color of the
suspension remained unchanged. The suspension was then reacted with
H2 under 25 psig pressure and 100°C. After reacting for 15 minutes
the formation of an orange solution was observed. No spectroscopic
evidence (infrared or % NMR) indicative of a rhodium hydride
ccrplex was detected. Upon addition of 1-hexene to the orange

158
solution the hydrogenation of 1-hexene was detected. Investigation
of the resulting solution by infrared spectroscopy and % NMR showed
no evidence for the presence of a rhodium hydride complex. These
results suggest that the activation of hydrogen may be the difficult
step in the reaction. Once a hydrido species is formed, facile
reaction with the olefin is proposed to occur yielding an alkyl
intermediate. Insita infrared studies were used to investigate the
hydroformylation of 1-hexene with a series of RhH(GO) 2 (ER3) 2
complexes and resulted in facile formation of rhodium alkyl
complexes while no hydride band was detected.141 Similar chemistry
is proposed to occur in the systems studied in this work.
Complexes of the general formula, Rh(PFh3)3X have also been
shown to decarbonylate aldehydes.134»98 Upon reaction of an orange
suspension of Kh(C>2CCF3) (FFh3)3 in benzene with heptaldehyde at 25°C
no change in the suspension were observed. Upon warming the
suspension to 40°C, the formation of a yellow solution was observed
similar to those reported in the literature.98 Characterization of
the solution by infrared spectroscopy shewed the presence of
absorbances at 1980 and 1689 cm”1 assigned to a carbonyl and
asymmetric carboxylate stretch respectively. These results suggest
a slew (relative to the facile reaction of Rh(02CCF3) (Plh3)3 with
CO) decarbonylaticn of aldehydes as shown in Ecjuation 3-18. The
rch2cho
Rh(02CCF3) (PFh3)3 > Rh(02CCF3)00(PEh3)2 + PPh3 (3-18)
hydrocarbon product formed after decarbonylation was not
investigated though it is proposed to be heptane.

159
Proposed Mechanism for the Catalytic Hvdroformvlation of 1-Hexene
with Kh(CbCCF3) (PEh3) 3 and Added TriphenvltAiosdiine
The proposed mechanism for the hydroformylation of olefins
catalyzed by the rhodium trifluoroaoetate triphenylphosphine system
is believed to consist of two sets of reactions. One set of
reactions involves the reaction with carbon monoxide upon
dissociation of triphenylphosphine from Rh(C>20CF3) (PPh3)3 as shown
in Equation 3-19. The addition of excess triphenylphosphine to
Fh(02CCF3) (PFh3)3 + CD < > Ih(02CCF3)00(Pih3)2 + PFh3 (3-19)
the catalyst system would be expected to shift the equilibrium in
Equation 3-19 toward the side of the tris (phosphine) complex. The
dissociation of phosphine to yield a bis (phosphine) complex is
supported from the 31P NMR data. The presence of a bis (phosphine)
complex may be the active catalyst or precursor. It is possible
that the tris (phosphine) complex is catalyzing the hydroformylation
reaction and that dissociation of the trifluoroaoetate ligand
occurs. This would open a coordination site on the rhodium center
for the binding and subsequent activation of reactants. This type
of carboxylate dissociation reaction may represent an alternative
pathway for the hydroformylation.
The next set of reactions in the scheme specifically involve
the hydroformylation of olefins as shewn in Figure 3-22. In the
Rh(C>20CF3) (FFh3)3 system, the initial formation of a rhodium hydrido
carbonyl complex is proposed to occur, unlike the RhH(CO) 2 (PPh3) 2
system where those ligands are present on the catalyst precursor.

160
PPh3
F3CCO,— Rh — PPh,
CO
Figure 3-22. Proposed Mechanism for the Hydroformylation
of Olefins with the Tris (triphenylphosphine)
Rhodium(I) Trifluoroacetate System.

161
Activation of dihydrogen and coordination of carbon monoxide are
proposed to occur at the onset of the reaction. For the
Fh(020CF3) (PTh3)3 system it was shewn that coordination of 00 occurs
readily even at ambient pressure and temperature. It is proposed
that the coordination of CD and H2 occur upen loss of PPh3 from the
tris (phosphine) complex to produce a species best formulated as
Rh(02CCF3) (00) (FEh3) 2H2. The identification of a rhodium hydride
species has never been observed in this work suggesting that once
formed, the hydrido is unstable and undergoes rapid reaction.
In the presence of an olefin, the formation of an alkyl
complex, Rh(020CF3) (00) (PFh3)2 (alkyl)H, is proposed to occur. This
is proposed to be the rate determining step in the reaction. The
increased activity observed with the perfluorocarboxylate complexes
compared with the rhodium hydrido system is consistent with this
proposed.. For RhH(OO) (PPh3)3 catalyzed hydroformylations, this step
has been proposed as rate determining.116 The formation of branched
alkyl intermediates (and eventually branched aldehyde products)
would occur from the mode of olefin coordination at the rhodium
hydride complex (Markovnikov versus anti- Markovnikov). The
formation of hexane would occur from direct hydrogenation of the
alkyl species.
The next step in the mechanism is proposed to be CO migratory
insertion to yield an acyl species. During this step coordination
of PFh3 is proposed to occupy the vacant coordination site available
after 00 migration. The presence of excess PEh3 in the system would
be expected to drive this reaction toward the acyl species.

162
Reductive elimination of the aldehyde product would be the last step
in the reaction to complete the cycle and regenerate the catalyst,
Rh(C>2CCF3) (PFh3) 3. The sequence of steps proposed in this
mechanistic scheme are reasonable based upon the proposed mechanism
discussed at the beginning of this chapter for the hydroformylation
of olefins with the RhH(00)2(Pfh3)2 system.112'113
D. Summary
In this study the investigation of rhodium (II) carboxylate
complexes as catalysts for the hydroformylation of olefins was
initially undertaken. The flourinated carboxylate
(perfluorobutyrate and trifluoroacetate) complexes were found to
exhibit high activity and stability for the hydroformylation of 1-
hexene to heptaldehyde. The addition of triphenylphosphine to the
reaction resulted in a marked increase in both the overall activity
of the system for hydroformylation and selectivity for the
production of the linear aldehyde product.
The rhodium perfluorobutyrate system was found to exhibit
greater activity and selectivity for the hydroformylation of 1-
hexene than the rhodium(II) trifluoroacetate system. The increased
activity observed with the perfluorobutyrate complex is proposed to
be related to its reported increased ability to bind olefins better
than the rhodium trifluoroacetate complex. Comparative studies with
typical rhodium(I) hydroformylation catalysts were conducted and

163
they displayed similar activity as the rhodium (II)
perfluorocarboxylate-tripheny lphosphine system.
Spectroscopic studies were undertaken to probe the stability
of the rhodium (II) perflourocarboxylate dimers under catalytic
conditions and in the presence of added triphenylphosphine.
Infrared and NMR data support the formation of a rhodium(I)
carboxylate triphenylphosphine complex during the hydroformylation
reaction. Continued investigation of the system resulted in the
determination that upen addition of phosphine to the rhodium dimer
dissociation of the complex occurred. The addition of the reactant
1-hexene did not result in cleavage of the rhodium dimer which was
shown to remain intact by visible spectroscopy.
To get a better understanding of the hydroformylation system,
studies were conducted to synthesize, characterize and investigate
the activity of the complexes formed upen addition of excess
triphenylphosphine to the rhodium(II) carboxylate complexes. With
the rhodium (II) trifluoroacetate complex, the addition of excess
FEh3 resulted in the formation of an orange solid whose
characterization supported Rh(020CF3) (FFh3)3. Other synthetic
routes also supported the formation of tris (triphenylphosphine)
rhodium(I) trifluoroacetate. A number of preparations were
investigated for the formation of the perfluorobutyrate analog. In
each case a pure solid could not be isolated. It is preposed that
the isolation of this complex and subsequent investigation of its
activity for hydroformylations would result in an active catalyst
system.

164
The rhodium trifluonoacetate triphenylphosphine complex was
investigated for catalytic activity for the hydroformylation of 1-
hexene. This complex was found to exhibit catalytic activity
comparable to that observed with the rhodium (II) trifluoroacetate
phosphine system. The addition of excess triphenylphosphine also
resulted in an increase in the catalyst activity and selectivity for
the formation of heptaldehyde.
Spectroscopic techniques were used to investigate the species
formed in solution during hydroformylation. Infrared and NMR data
obtained suggest the formation of a bis (triphenylphosphine)
rhodium(I) trifluoroacetate carbonyl species. The preparation and
characterization of bis (triphenylphosphine) rhodium(I)
trifluoroacetate carbonyl was conducted and exhibited similar NMR
data as that obtained for the tris (phosphine) complex. The complex
was investigated for hydroformylation and was found to be active
supporting the formation of a bis (phosphine rhodium (I) carboxylate
carbonyl complex as the active catalytic species or precursor.
To probe the catalytic activity of the Rh(C>2CCF3) (PPh3) 3
system comparative studies were undertaken with RhH(CO) (PPh3) 3 which
is commonly employed for low pressure hydroformylation. In the
absence of added triphenylphosphine the trifluoroacetate was only
slightly more active than the hydrido complex (50 TON versus 38
TON). Upon addition of excess triphenylphosphine the differences in
activity are more pronounced. The trifluoroacetate system exhibited
225 TON while the hydrido system exhibited only 100 TON under
comparable reaction conditions. In both system the isomer ratio was

165
4.3 in the presence of 5 times added FEh3. Hie increased activity
observed in the rhodium trifluoroacetate system is attributed to the
presence of the electron-withdrawing carboxylate ligands. These
groups would be expected to increase the Lewis acidity of the
rhodium center and enhance its ability to coordinate and activate
the reactants. In both systems it is proposed that bis (phosphine)
complexes are active catalysts which would exhibit similar steric
influences hence the same observed isomer ratio.
This study has shewn that the rhodium perfluorocarboxylate
complexes exhibit high activity for the hydrofonnylation of 1-
hexene. The investigation of this system has resulted in the
identification of different catalytic species previously unreported.
The incorporation of perfluorocarboxylate ligands into other
organcmetallie complexes used in homogeneous catalysis cxiuld render
those complexes more active and should be investigated.

IV. OONdJUSION
This research was focused on the investigation of metal
complexes as catalysts for the indirect transformation of synthesis
gas into chemicals. The feasibility of developing catalytic systems
which operate under mild reaction conditions was investigated. Both
heterogeneous systems and homogeneous systems were studied. The
stability of the metal complexes during reaction was also probed.
The first study was focused chi the investigation of supported
iridium carbonyl clusters as potential catalysts for the reaction of
H2, GO and HC1 to selectively produce methyl chloride. As described
earlier, the development of a system based upon synthesis gas would
be of industrial importance. The initial research was focused on
the investigation of a phosphine substituted supported iridium
carbonyl system previously studied in our research group.40'44
Through a series of controlled experiments, it was discovered that
organic residues introduced into the system during preparation
caused misleading results during reaction with H2, 00 and HC1.50
The presence of these residues contributed to the formation of alkyl
halides making it difficult to discern whether methyl chloride was
produced from the reduction of carbon monoxide or from the
deccrposition of organic residues.
166

167
To eliminate the uncertainties encountered in the previous
iridium system, the carbonyl cluster was directly deposited on to
the oxide support. Supported iridium carbonyl was also reacted with
aluminum chloride for the purpose of establishing a system where
bifunctional activation of carbon monoxide could occur. It was
hoped that this combination of a carbonyl cluster and Lewis acid
would lead to the development of a system capable of reduction of
carbon monoxide under mild reaction conditions. The iridium
carbonyl-aluminum chloride system was proposed to be a heterogenized
analog of a homogeneous system studied by Muetterties5 and Coliman.6
The supported iridium carbonyl clusters were investigated by
infrared spectroscopy in order to get a better understanding of the
interaction of the cluster with the support and Lewis acid.
Spectroscopic data suggest adsorption of the intact cluster on the
surface of the support. Upon reaction with aluminum chloride, data
suggest an interaction of the cluster with the Lewis acid sites
present on the surface of the support.
The deposited iridium carbonyl clusters were investigated for
reaction with H2, 00 and HCl(g) at 125°C and 1 atmosphere pressure.
The major product formed was methyl chloride. Other products
detected include methane, carbon dioxide, water and minor C2
products. The homogeneous analog exhibited high selectivity for the
formation of ethane while only forming minor amounts of methyl
chloride. The high selectivity for the formation of methyl chloride
in the heterogeneous system is attributed to the presence of HC1 (g)
in the reactant feed which would convert intermediates directly

168
to methyl chloride prior to further homologation and hydrogenation
leading to higher products. The heterogenized system investigated
in this study does not appear to be catalytically reducing carbon
monoxide to methyl chloride. A major pathway for the formation of
products is proposed to involve the decomposition of the iridium
carbonyl cluster. Infrared spectroscopy was used to investigate the
materials after reaction and suggests the transformation of the
cluster to a multinuclear species and not to metallic iridium. The
resulting materials were no longer active for the reduction of
carbol monoxide. This study has shewn that the development of a
catalyst for the formation of methyl chloride from synthesis gas is
not feasible based upon a system employing iridium carbonyl and
aluminum chloride. The reactivity of the cluster with the support,
aluminum chloride and the reactant gases may seme day aid in a
better understanding of the chemical transformations which can occur
on the way to forming an active catalyst.
In the second study, a rhodium carboxylate triphenylphosphine
catalyst was developed for the hydroforrnylation of olefins under
mild reaction conditions. The family of rhodium(II) carboxylate
dimers was initially studied for the hydroforrnylation of 1-hexene.
The effect of the carboxylate ligand and the addition of
triphenylphosphine as a promoter on the hydroforrnylation activity
and oenplex stability was investigated. The perfluorocarboxylate
dimers were found to exhibit high activity and remain homogeneous
throughout the reaction unlike their nonfluorinated analog which
decomposed during hydroforrnylation. The fluorinated dimers have

169
been reported to exhibit enhanced properties for the binding of
molecules compared to their nonfluorinated analog.83'89
Spectroscopic studies were undertaken to investigate the stability
of the rhodium dimers during reaction and to determine the nature of
the active species. Data obtained support cleavage of the rhodium
dimer upon addition of triphenylphosphine to produce mononuclear
rhodium perf luorocarboxylate phosphine complexes which exhibited
activity for the hydroformylation of 1-hexene.
To obtain a better understanding of the species formed upon
addition of triphenylphosphine to the rhodium perfluorocarboxylate
dimers and their reactivity for the hydroformylation of 1-hexene;
the preparation, characterization, and catalytic investigation of
these ccnplexes was undertaken. Upen addition of triphenylphosphine
to rhodium(II) trifluoroacetate, tris (triphenylphosphine) rhodium(I)
trifluoroacetate was formed. This complex exhibits high activity
for the hydroformylation of 1-hexene to heptaldehyde. The addition
of triphenylphosphine resulted in an increase in both the activity
and selectivity of the system for the formation of the linear
product. Comparative studies were undertaken with a commercial
rhodium hydroformylation catalyst, RhH(CO) (PPh3) 3. The rhodium
trifluoroacetate exhibited higher activity and greater stability
than the rhodium hydrido system. Upon addition of
triphenylphosphine, these differences become more pronounced. The
increased activity of the trifluoroacetate system compared with the
hydrido system is attributed to the presence of the electron-
withdrawing fluorinated carboxylate ligands making the rhodium

170
center a better Lewis acid for the binding and activation of the
reactants. A study of the species formed during hydroformylation
yielded data suggesting the presence of a bis (triphenylphosphine)
rhodium(I) carbonyl tri f luoroacetate carp lex.
Preliminary studies were undertaken to develop a
heterogeneous analog of the homogeneous rhodium trifluoroacetate
phosphine system. The complex was supported onto a fluorocarbon
polymer leached off during hydroformylation yielding the homogeneous
system. A solid-gas phase system was also investigated for the
hydroformylation of propylene. The rhodium trifluoroacetate complex
was encapsulated in a polymeric membrane film and used in a pressure
differential reactor. The system exhibited high activity for the
hydroformylation of propylene to butyraldehyde with no branched
aldehyde being detected. These results are encouraging and suggest
that continued study and development of this type of a heterogenized
system should be conducted. Finally, the investigation of the
rhodium trifluoroacetate system has allowed for the study of new
catalytic species previously unreported to be active
hydroformylation catalysts. Other metal perfluorocarboxylate
complexes should be investigated for different catalytic reactions
involving the binding of olefins such as oxidations.

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BIOGRAPHICAL SKETCH
The author was bom in New York, New York, and grew up outside
of Albany in Delmar. She attended Bethlehem Central High School and
graduated in 1976. In 1980, she graduated cum laude from the State
University of New York at Plattsburc^i with a B.S. in chemistry.
During her studies at Plattsburgh she had the opportunity to
participate in an undergraduate research program. She attended
graduate school at the University of Florida in Gainesville,
Florida. Her area of concentration was inorganic chemistry and
studied under the guidance of Russell S. Drago. While attending
graduate school she married a fellcw classmate, Edward Getty. Upon
ccnpletion of her graduate studies she will begin her career with
The Drackett Company in Cincinnati, Ohio. The author has published
several papers and has applied for a patent.
179

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.
Graduate Research Professor
of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.
David E. Richardson
Assistant Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.
/ f; ( /
Harrv tf. /is/ler
nstingu/shed Service Professor
of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.
John GJ. Dorsey
Asso^-fate Professor of Chemistry

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.
Gar B. Hoflund u
Professor of Chemical Engineering
This dissertation was submitted to the Graduate Faculty of the
Deaprtment of Chemistry in the College of Liberal Arts and Sciences
and to the Graduate School and was accepted as partial fulfillment
of the requirements for the degree of Doctor of Philosophy.
December 1988
Dean, Graduate School

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