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Design and Synthesis of Early Transition Metal Trianionic Pincer Ligands

Permanent Link: http://ufdc.ufl.edu/UFE0021496/00001

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Title: Design and Synthesis of Early Transition Metal Trianionic Pincer Ligands
Physical Description: 1 online resource (79 p.)
Language: english
Creator: Carlson, Adam R
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2007

Subjects

Subjects / Keywords: early, high, ligand, metal, molybdenum, oxidation, pincer, state, titanium, transition, trianionic, zirconium
Chemistry -- Dissertations, Academic -- UF
Genre: Chemistry thesis, M.S.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Chemical catalysis is an efficient method of forming more complex chemicals used in pharmaceuticals and industry. Innovative catalyst design leads to reduced waste and energy use resulting in lower production cost and ultimately lower cost to the end consumer. Catalysts require the use of metals, many of which are expensive. Incorporation of less expensive metals into catalytic systems offers significant cost lowering benefits. Until recently the reactivity of less expensive metals has not been explored as alternatives in catalysis. My research explores new designs and expansion of current methods needed to form these new catalysts.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Adam R Carlson.
Thesis: Thesis (M.S.)--University of Florida, 2007.
Local: Adviser: Veige, Adam S.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2007
System ID: UFE0021496:00001

Permanent Link: http://ufdc.ufl.edu/UFE0021496/00001

Material Information

Title: Design and Synthesis of Early Transition Metal Trianionic Pincer Ligands
Physical Description: 1 online resource (79 p.)
Language: english
Creator: Carlson, Adam R
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2007

Subjects

Subjects / Keywords: early, high, ligand, metal, molybdenum, oxidation, pincer, state, titanium, transition, trianionic, zirconium
Chemistry -- Dissertations, Academic -- UF
Genre: Chemistry thesis, M.S.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Chemical catalysis is an efficient method of forming more complex chemicals used in pharmaceuticals and industry. Innovative catalyst design leads to reduced waste and energy use resulting in lower production cost and ultimately lower cost to the end consumer. Catalysts require the use of metals, many of which are expensive. Incorporation of less expensive metals into catalytic systems offers significant cost lowering benefits. Until recently the reactivity of less expensive metals has not been explored as alternatives in catalysis. My research explores new designs and expansion of current methods needed to form these new catalysts.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Adam R Carlson.
Thesis: Thesis (M.S.)--University of Florida, 2007.
Local: Adviser: Veige, Adam S.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2007
System ID: UFE0021496:00001


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DESIGN AND SYNTHESIS OF EARLY TRANSITION METAL
TRIANIONIC PINCER LIGANDS



















By

ADAM RAND CARLSON


A THESIS PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF SCIENCE

UNIVERSITY OF FLORIDA


2007


































O 2007 Adam Rand Carlson



































To my mom









ACKNOWLEDGMENTS

I thank Dr. Adam Veige and the entire Veige Group for their support. I would also like

to thank Dr. Khalil Abboud for my crystal structure data. I thank my parents for their loving

encouragement, which motivated me to complete my study.











TABLE OF CONTENTS


page

ACKNOWLEDGEMENT S ................. ...............3.......... ......

LI ST OF T ABLE S ................. ...............7................

LI ST OF FIGURE S .............. ...............8.....

LIST OF SCHEMES............... ................ 10

LI ST OF AB BREVIAT IONS ................. ................. 11......... ...

AB STRAC T ................ .............. 12

CHAPTER

1 INTRODUCTION .............. .................... 13


Classic Pincer Ligands ................. ................. 13......... ....
Features of Pincer Ligands .............. ....._._ .............._ 13..
Examples of Pincer Ligands in Chemistry. .....___.....__.___ .......____ ...........1
Previous Trianionic Pincer Results ............... ... .. .......... ................. ...............1
Modification of NCN Trianionic Pincer Ligands and New Metallation Schemes ........... 1 5

2 SYNTHESIS AND REACTIONS OF NcCcN PINCERS .............. .................... 19


Synthesis and Characterization of [2,4,6-MeArNcCcN]H3 (3)
and [3,5-CF 3NcCc N]H 3 (4)....................................................... 19
Synthesi s and Characterizati on of CI-(2,6-'PrNCN) [Zr(N\M e2)3] 2 o
and [ p(3,5-CF3NCCcN)Zr(NMe2)2 6Iv~z)2) 27) .........._._.........._ .... ...... ........ 20
Synthesis and Characterizati on of pu-(3,5-CF3NcCcN))[Mo(N\M e2) 3 2 (8)....................... 2 1
Synthesis and Characterization of [3,5-CF3NcCcN]Mg(THF)2 (10) ............... ... .........._.21
Synthesis and Characterization of [3,5-CF3 C CN] TMS2H (11) ................. ................22
Conclusions ................. ................. 24..............
Experim ental ................. ............ ................. 24...
General Considerations ................... .... ........ .......... ............ 2
Synthesi s of 2,2'-(1,3 -phenyl ene)diethanamine (2) ................. ............ ........ 25
Synthe si s of N,N'r-(2,2'-(1,3 -phenyl ene)bi s(ethane-2, 1-diyl))
bis(2,4,6-trimethylaniline) (3).................... .. ..................... 25
Synthe si s of N,N'r-(2,2'-(1,3 -phenyl ene)bi s(ethane-2, 1-diyl))
bis(3,5-bi s(trifluoromethyl)aniline) (4) ........._....... ......._._ ......._........ 26
Synthesis of [p-(3,5-CF3NcCcCN)Zr(NMe2)3 8~2 2 (7) ..........._. ............._._ 27
Synthesis of pu-(3,5-CF3NCcC cN)[Mo(NMe2)3 2 (8) ........ .............. 27
Synthesis of [p-(3 ,5-CF3NcCcN]HMg(THF)2 (10) ................. ......._._. ....... 28
Synthesis of [3,5-CF3NcCcN]H(SiMe3) 2 (11) ................. .......... .............. 28











page


X-ray Experimental Details For [3,5-CF3-NcCcN]H3 (4) ..............~~~ ..............~ 29
X-ray Experimental Details For pu-(2,6-'PrNCN)[Zr(NMe2)3 2 (6) ..................... 30
X-ray Experimental Details For [p-(3,5-CF3NcCcN)Zr(NMe2)3 8~2 2 (7).... 30
X-ray Experimental Details For [p-(3 ,5-CF3NcCcN]HMg(THF)2 (10).............. 31

3 SYNTHESIS AND REACTIVITY OF TERPHENYL
OCO3- PINCER COMPLEXES .............. .................... 55


Synthesis and Characterization of terphenyl [tBuOCO]H3 (17) ........._.__.... ......_. .....55
Synthesis and Characterization of [tBuOCO]MONMe2(HNMe2)2 (18).............._._. ......... 56
Synthesis and Characterization of [tBuOCO]MoCl (19) ........._.__...... ._ .............57
Conclusions ........._.__...... ..__. .............._ 58...
Experimental .........._.... .......__. .............._ 58...
General Considerations ........._._......... .._ ...... .............. 58
Synthesis of 2-bromo-6-tert-butylphenol (13) .........._.... .......___ ........_._.... 59
Synthesis of 1-bromo-3 -tert-butyl-2-methoxybenzene (14) .........._.... ............. 59
Synthesis of 1,3 -dibromo-2-iodobenzene (15) .........._......... .. .._._ ................. 60
Synthesis of 3,3"-di-tert-butyl-2,2"-dimethoxy- 1,1':3',1l"-terphenyl (16)........... 60
Synthesis of 3,3"-di-tert-butyl- 1,1':3',1"
-terphenyl-2,2"-diol ([tBuOCO]H3) (17) ................. ......... ................ 60
Synthesis of [tBuOCO]MONMe2(HNMe2)2 (18) ................. ................ ...._ 61
Synthesis of [tBuOCO]Mo(HNMe2)2Cl (19) .................. ............. ...... ................ 62
X-ray Experimental Details For [tBuOCO]MONMe2(HNMe2)2 (18) .................. 62
X-ray Experimental Details For [tBuOCO]Mo(HNMe2)2Cl (19) ................... ..... 63

LIST OF REFERENCES ................. ..............76................

BIOGRAPHICAL SKETCH ................. ..............79.......... ......









LIST OF TABLES


Table Page


2-1 Selected angles and bond lengths for crystal structures 6, 7, and 10............... ............... 59

2-2 Crystal data, structure solution and refinement for [3,5-CF3NcCcN]H3 (4) ................... 51

2-3 Crystal data and structure refinement for pu-(2,6-'PrNCN) [Zr(NMe2)3 2 (6)................... 52

2-4 Crystal data and structure refinement for
[CI-(3,5-CF3NcCcN)Zr(NMe 2)3HNMe 2 2 (7)................... .............. 53

2-5 Crystal data and structure refinement for [pu-(3 ,5-CF3NcCcN]HMg(THF)2 (10) ........... 54

3-1 Selected angles and bond lengths for crystal structures 18 and 19............... ................. 73

3-2 Crystal data and structure refinement for [tBuOCO]MONMe2(HNMe2)2 (18)................. 74

3-3 Crystal data and structure refinement for [tBuOCO]Mo(HNMe2)2Cl (19)....................... 75










LIST OF FIGURES


Figure Page

1-1 Format of classic pincer ligands .............. .................... 17

1-2 Pincer catalyzed reactions ........._. ....... .__ .............. 17...

1-3 Monoanionic "Soft-Hard-Soft" and trianionic
"Hard-Hard-Hard" pincer binding motifs. ................................... 17

1-4 POV-ray diagram of 2,6-'PrArNCN-Zr and 2,6-'PrArNCN-Ti ........... ..............__ 18

2-1 ORTEP diagram of [3,5-CF3NcCcN]H3 (4)............... ..............~~~~ 34


2-2 ORTEP diagram of (2,6-'Pr-NCN) [Zr(N\Me2)3 2 (6) .............. .............. 35

2-3 ORTEP diagram of pu-(3,5-CF3-NcCcN)[Zr(NMe2>2(HNMe2> 2 (7)............_. ............_ 36

2-4 ORTEP diagram of [pu-(3,5-CF3NcCcN]HMg(THF) 2 (10)............_.._. ........__. ....... 37

2-5 1H NMR spectra of 2,2'-(1,3 -phenylene)diethanamine (2) in C6D6 ........ .............. 38s

2-6 1H NMR spectra of [2,4,6-MeNcCcN]H3 (3) 111 C6D6........ .............. 39

2-7 1H NMR spectra of [3,5-CF3NcCcN]H3 (4) in C6D6 .............. .............. 40

2-8 13 g lH} NMR spectrum of [3,5-CF3NcCcN]H3 (4) in C6D6 .............. .............. 41

2-9 1H NMR spectra of [pu-(3,5-CF3NcCcN)Zr(NMe2)3HNMe2 2 (7) 111 C6D6 ..................... 42

2-10 13 g lH} NMR spectrum of [pu-(3,5-CF3NcCcN)Zr(NMe2)3HNMe2 2 (7) in THF-d8...... 43

2-11 1H NMR spectra of pu-(3, 5-CF3NcCcN)[Mo(NMe2)3 2 (8) 111 C6D6........ .............. 44

2-12 13C t 1H} NMR spectrum of pu-(3 ,5-CF3NcCcN)[Mo(NMe2)3 2 (8) 111 C6D6 .................... 45

2-13 1H NMR spectra of [3,5-CF3NcCcN]HMg(THF)2 (10) in Tol-ds @ -75 OC .................... .46

2-14 1H NMR spectra of [3,5-CF3NcCcN]H(SiMe3)2 (11) 111 C6D6 .............. .............. 47

2-15 13 1H NMR spectrum of [3,5-CF3NcCcN]H(SiMe3)2 (11) 111 C6D6..................... 48

2-16 19F NMR spectrum of [3,5-CF3NcCcN]H(SiMe3)2 (11) 111 C6D6 .............. .............. 49

3-1 ORTEP diagram of [tBuOCO]MONMe2(HNMe2)2 (18)............... ............. .... 65










Figure page

3-2 ORTEP diagram of [tBuOCO]Mo(HNMe2)2Cl (19) .............. ................. ... 66

3-3 1H NMR spectrum of [tBuOCO]H3 (17) in acetone-d6................ .............. 67

3-4 13C NMR spectrum of [tBuOCO]H3 (1)iC6D6 .............. .................... 68

3-5 1H NMR spectrum of [tBuOCO]MONMe2(HNMe2)2 (18) in THF-d8 .............. .... .......... 69

3-6 13C NMR spectrum of [tBuOCO]MONMe2(HNMe2)2 (18) in THF-ds ................... .......... 70

3-7 1H N\MR spectrum of [tBuOCO]Mo(HNMe2)2C (9) n C6D6........ .............. 71

3-8 13C NMR spectrum of [tBuOCO]Mo(HNMe2)2Cl (19) in THF-ds............... .................72










LIST OF SCHEMES


Scheme page

1-1 Formation of group 4 NCN metal complexes ................. ................. 16...........

1-2 Metallation via trimethylsilyl-halide elimination .............. .................... 16

1-3 Metallation via amine extrusion................ .............. 16

2-1 Synthesis of ArNcCcNH3 (where Ar = 2,4,6-MeC6H3 (3) and 3,5-CF3 6H3 (4))........... 32

2-2 Synthesis of 6 and 7 (where Ar = 2,4-'PrC6H3 (6) and 3,5-CF3 6H3 (7) ................... ...... 32

2-3 Synthesis of the mol bdenum dinuclear species
pu-(3,5-CF3NcC N) [Mo(NMe2)3 2 (8) ................. ................. 33............

2-4 Synthesis of the dimagnesio salt [3,5-CF3 CCN]H[MgCl(THF)2 2 (9) and the
minor impurity monomagnesio salt [pu-(3 ,5-CF3NcCcN]HMg(THF)2 (10) .............. 33

2-5 Synthesis of the bistrimethylsilyl species [3,5-CF3NcCcN]H(SiMe3)2 (11) ................... 33

3-1 Synthesis of [tBuOCO]H3 (17) .............. .................... 64

3-2 Synthesis of [tBuOCO]MONMe2(HNMe2)2 (18) ................ .............. ....__. ..... 64

3-3 Synthesis of [tBuOCO]Mo(HNMe2)2Cl (19) ................. ................. 65......... ...









LIST OF ABBREVIATIONS


ECE electron donor-carbon-el ectron donor pincer ligands

e- electron

M-C a metal-carbon bond

'Pr iso-propyl

tBu tert-butyl

EDG electron donating group

EWG electron withdrawing group

PCP pho sphorou s-carb on-pho sphorou s

NCN nitrogen-carbon-nitrogen pincer ligands

OCO oxygen-carbon-oxygen pincer ligand

NMR nuclear magnetic resonance

HRMS high resolution mass spectrometry









Abstract of Thesis Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Master of Science

DESIGN AND SYNTHESIS OF EARLY TRANSITION METAL
TRIANIONIC PINCER LIGANDS

By

Adam Rand Carlson

December 2007

Chairman: Adam Veige
Major: Chemistry

The chemistry of trianionic pincer ligands is largely unknown, but preliminary synthetic

studies establish their terdentate coordination behavior. Early transition metals differ greatly in

reactivity and coordination compared with late transition metals. Classic pincer ligands have

been designed for use with "soft" late transition metals and are not well suited for early transition

metals. New trianionic pincer ligands utilize a "hard-hard-hard" binding motif, which is more

suitable for "hard" early transition metals. Appropriate conditions for coordination of trianionic

pincer ligands to early transition metals must be developed. Pincer ligands are easily modified

and are not limited to a single method of metallation. This thesis describes the synthesis and

reactivity of new trianionic pincer ligands NCN3- and OCO3- with group 4 and 6 early transition

metals.









CHAPTER 1
INTRODUCTION

Classic Pincer Ligands

The first mention of a pincer ligand in the literature was by Shaw in 1976. He described

a PCP pincer review coordinated to rhodium(III), iridium(III), palladium(II) and platinum(II)

(group 9 and 10) metal ions.l~ Pincer ligated metal complexes, when used in homogeneous

metal catalysis, can promote efficient chemical transformations. Today these complexes are

used with great success in a wide range of industrial and fmne chemical syntheses.6-13

Features of Pincer Ligands

Pincer ligands share two salient features, the most important being the presence of a

central metal-aryl o-bond. This metal-carbon (M-C) bond renders complexes thermally robust

and prevents dissociation from the metal even at high temperatures, leading to high turnover

numbers. This M-C bond carries a single negative charge, making the maj ority of pincer ligands

monoamiomc.

The second characteristic of classic pincer ligands is the presence of two neutral, two

electron donor atoms attached via methylene spacers at the 2- and 6-positions of the aryl

backbone. Tertiary phosphines such as those first used by Shaw were initially used as donor

atoms, but the incorporation of other neutral 2e- donors (Figure 1-1) into the structure has led to

the complexation of a wide range of transition metals.14 These two electron donors are typically

denoted as "E", making the abbreviation for pincer ligands "ECE". The pendant arms can be

altered to enable control of electron density at the metal. The terdentate binding of a pincer

ligand to metals increases the stability of the organometallic complex relative to mono or

bidentate ligands. The terdentate motif also serves to enable greater control over accessibility to

the metal, and therefore substrate binding, since the ligand occupies three coordination sites.









Further tailoring of this modular architecture by the addition of electron withdrawing (EWG) or

electron donating (EDG) groups to the aryl backbone can fine-tune the electron density at the

metal. 1

Examples of Pincer Ligands in Chemistry

The variety of chemical transformations that can be catalyzed by pincer ligand systems is

beyond the scope of this thesisl6 but a few examples are shown below (Figure 1-2).17~1 These

reactions include poly-olefin,19 alkane and cycloalkane dehydrogenation, Suzuki couplings,20

Heck reactions, aldol reactions, cyclopropanations, allylation of alcohols, allylic alkylation,

hydrogenation of ketones, Kharasch additions,21 and Michael reactions.

To date the maj ority of useful pincer related catalysts have used the expensive late

metals. The main obj ective for this project is to tailor a pincer ligand so that it will

accommodate the specific demands of cheaper early transition metals. The problem with using a

classic pincer ligand design to form an early transition metal complex, is that early and late

transition metals differ significantly in their properties. Generally, late transition metals favor

low oxidation states, are low coordinate and are tolerant of many functional groups.22-25 By

contrast, early transition metals favor high oxidation states and are intolerant of many functional

groups. In a classic pincer ligand, the interaction between the pendant arms and the metal is a

lone-pair donation, considered as a "soft" delocalized interaction. By comparison, the anionic

carbon is considered "hard" giving classic pincer ligands a "soft-hard-soft" interaction with a

metal center. This is ideal for late transition metals, which are considered "soft", but the

interaction is not preferred by early transition metals, which are considered "hard".

The hard nature of the early transition metals necessitates modification of the pincer

ligand from its traditional monoanionic "soft-hard-soft" design to a trianionic "hard-hard-hard"









binding motif (Figure 1-3). This hard donation can be accomplished via a localized electron pair

donation of an anionic "hard" atom such as C-, N-, or O-. Because early transition metals are

electro-positive this hard interaction stabilizes higher oxidation states. A trianionic pincer

ligand serves to occupy three coordination sites of the metal and at least stabilize oxidation state

of 3 As with late transition metal pincer systems a halide transrt~t~rt~t~rt~t~rt~ to the M-C bond serves to

promote functionalization of the complex, or allow for entry into various catalytic cycles. This

halide contributes to produce a 4+ oxidation state with a trianionic pincer ligand. The 4+

oxidation state is common for our target group 4 and 6 metals.

Previous Trianionic Pincer Results

The first generation trianionic pincer ligands successfully ligated all of the group 4 metals

(Ti, Zr, Hf) by using a trilithio salts of the parent NCN ligand (Scheme 1-1). However, when

applied to group 6 metals only intractable mixtures were produced. This was presumably due to

electron-transfer reduction of the metal substrate. Early transition metals are especially

susceptible to these side reactions during R-Li salt metathesis. X-ray crystal structures of the

group 4 metal-NCN complexes did reveal very small N-M-N bond angles of ~1400 (Figure 1-4)

compared with N-M-N bond angles of ~1600 for late transition metals.26-2 Based on these

results we sought to make a change to the NCN pincer design, and explore alternative routes to

met all ati on.

Modification of NCN Trianionic Pincer Ligands and New Metallation Schemes

The first change needed was an increase in the length of the pendant arms from single

methylene spacers. Inserting an additional methylene spacer to form NcCcN derivatives would

produce two six-membered rings once chelated, but more importantly would allow for changes

in metal atomic radii during reaction sequences. The second change was a modification of our










approach to metallation. One of the benefits of using hard donor atoms is the ease of

functionalization thus enabling different metallation schemes. The donor atoms can be modified

to include functional groups such as SiMe3, which have been shown to eliminate

trimethyl silylhalides when reacted with metal halides.28 Thi s method serves to chelate the metal

followed by stepwise alkylation of the metal that can form the final M-C bond (Scheme 1-2).

While lithium salts were used successfully to ligate group 4 metals sodium and potassium salts

are an alternative for group 6 metals. In addition, protonated ligands can be reacted directly with

metal dialkylamides which eliminates dialkylamine (Scheme 1-3).


,Ar ,ATI


\ / Li THF \/Ml
SLi -3 5 o eCi
N'Ar NAr
Ar = 2,6-'PrC6H3 M = Ti, Zr, Hf

Scheme 1-1. Formation of group 4 NCN metal complexes.


,Ar
MCH M\x- Y
-2Me3SiCI /
N'Ar


,Ar
IN
MeMgCI, / \
M(Mex-3
N'Ar


Scheme 1-2. Metallation via trimethylsilyl-halide elimination.


,Ar ,Ar
N N
/ \ H M(N Me2>4
H \ / MNMe2
H -3 HNMe2 '
N'Ar N'Ar

Scheme 1-3. Metallation via amine extrusion.










I. E= E'= PR2
II. E=E'=NR2
Il.E=E'=AsR2
SE= E'= SR
VI. E=E'=0R
Vll. E= E'= SeR
Vlll. E= NR2, E'=PR2
E= OR, E'=PR2
Y= EWG, EDG


E I


Figure 1-1. Format of classic pincer ligands.


I+O





+


OO-














trans-stilbene


Ctl


Base
TON > 520,000



O-P' Pr2

d-CI

O-P' Pr2


Figure 1-2. Pincer catalyzed reactions.


"Soft-Hard-Soft"


" Ha rd-H ard- Hard "


Figure 1-3. Monoanionic "Soft-Hard-Soft" and trianionic "Hard-Hard-Hard" pincer binding
motifs.

















Fgre14 PVra dfiagramo 2,-P:rCNZ and 2,-PrC-i.
Seetd odagls 2ZrN 1010 N -iN = 14.46









CHAPTER 2
SYNTHESIS AND IVETALLATION OF NcCcN PINCER LIGANDS

Synthesis and Characterization of [2,4,6-MeArNcCCN]H3 (3) and [3,5-CF3NcCCN]H3 (4)

The most direct synthesis of our target NcCcN pincer ligands utilizes diamine 2. This

starting material allows for easy access to a variety of pincer ligands via cross-coupling with any

commercially available bromobenzene. Diamine 2 is not commercially available, but can be

synthesized by reduction of dicyano 1 with LiAlH4*29 Diamine 2 was obtained in 33% yield

following purification by distillation. The identity of 2 was verified by 1H NMR spectroscopy.

The two sets of methylene protons are observed as triplets that integrate to four protons each and

appear at 2.88 and 2.65 ppm. A corresponding broad singlet is observed at 1.01 ppm and is

ascribed to the two NH protons. Diamine 2 was then used in a Buchwald-Hartwig cross-

coupling reacti on30,31 with 1 -bromomesitylene or 3,5 -trifluoromethylb romob enzene to produce

ligand 3 and 4 in 61% and 33% yield respectively (Scheme 2-1).

A H NMR spectrum of 3 revealed the expected two sets of methylene protons as a

doublet of triplets at 3.08 ppm and a triplet at 2.80 ppm. The key feature of the spectrum for 3

are two singlets corresponding to the methyl groups in the 2, 4, and 6 positions which and appear

at 2.15 and 2.06 ppm in a 6:12 ratio respectively.

The 1H NMR spectrum of 4 is similar, as expected to 3. A doublet of triplets and triplet at

3.73 and 2.38 ppm are observed for the two sets of methylene protons. The most indicative peak

of the molecule is a singlet at 6.48 ppm corresponding to the four protons in the 2 and 6 positions

of the trifluoromethyl aryl rings. The unique position of this peak is used to monitor the

progression of metallation reactions. Although ligand 3 is as an oil, 4 is easily crystallized from

saturated pentane solutions. The increased crystallinity of 4 can be attributed to the

trifluoromethyl groups. The molecular structure, determined by X-ray crystallography is









presented in Figure 2-1 and shows a staggered xn-stacking arrangement of three trifluoromethyl

rings from two independent ligand molecules. A table of pertinent bond lengths and angles is

presented in Table 2-1. The combined spectroscopic analysis and X-ray experiment confirmed

the identity of 4.

Synthesis and Characterization of pu-(2,6-iPrNCN)[Zr(NMe2)3 2 (6)
and [p-(3,5-CF3NcCCN)Zr(NMe2)2 0H~2) 2 (7)

Previous work in the Veige group was centered on the NCN derivative 5 in which only

one methylene group is present in the pincer arm. When 5 is treated with Zr(NMe2)4 the

bimetallic complex 6 is formed (Scheme 2-2) which was characterized by X-Ray

crystallographyand the structure is presented in Figure 2-2. The zirconium remains in a

tetrahedral geometry with three coordination sites occupied by dimethylamide ligands. In

contrast ligation of Zr(NMe2)4 with 4 produced dimer 7 in which each ligand occupies an axial

and equatorial site of opposing metal centers. The molecular structure is presented in Figure 2-3.

One coordinated dimethylamide group remains and is located transrt~t~rt~t~rt~t~rt~ to the ligand amide bond.

The coordinated dimethylamine is distinguished from the amides by its tetrahedral geometry and

the remaining amides are planar. The zirconium center has a distorted trigonal bipyramidal

geometry, with the equatorial amides separated by 114.44(11)o to 122.10(10)o and the axial

nitrogen atoms lying 174.00(10)o apart (Table 2-1).

Although ligand 4 did not chelate the metal as hoped, some information was obtained

from the difference in reactivity between 4 and 5. Clearly by moving the alkyl groups to the 3,5

positions allowed for the formation of a symmetric dimer that contained two bridging ligands

whereas the sterically bulky 'Pr groups only allowed one ligand to bridge. The influence of alkyl

group size in reactions with Zr(NMe2)4 WaS also probed by Lappert and coworkers.32 A









compound analogous to 6, with 2,6-methyl groups was reported to dimerize and incorporate two

bridging ligands under similar reaction conditions.

Synthesis and Characterization of pu-(3,5-CF3NCCCN) [Mo(NMe2)3 2 (s)

Additional reactivity differences between 4 and 5 are observed when treated with

Mo(NMe2)4. Ligand 5 proved unreactive, even when heated to reflux in toluene for 18 hours.

The lack of reactivity with Mo(NMe2)4 is due to proximity and size of the 2,6-'Pr groups. By

comparison, treatment of 4 with Mo(NMe2)4 resulted in coordination of the amide groups to Mo.

While less than 2.5 equiv of Mo(NMe2)4 did not consume all of 4, a bimetallic product could by

detected by 'H NMR spectroscopy when 3 equivalents were employed (Scheme 2-3). After

heating the reagents at 40 OC for 4 d a product was isolated by removal of all volatiles in vacuo

and then subliming the remaining Mo(NMe2)4. The product is tentatively assigned as the

bimetallic complex pu-(3,5-CF3NCN) [Mo(NMe2)3 2 (8) and is characterized by 1H NMR

spectroscopy. The two sets of methylene protons appear as triplets at 3.73 and 2.84 ppm. A

large singlet at 3.08 ppm that integrates to 36 protons is assigned to the methyl protons of 6

equivalent dimethylamide ligands. This supports the assignment of two molybdenum atoms that

coordinate 3 equivalent dimethylamides each, as in the crystallographically determined structure

of 6 above.

Synthesis and Characterization of [3,5-CF3NCCCcN]Mg(THF)2 (10)

To avoid the slow reactivity with metal dialkylamides we investigated a

trimethyl silylhalide (TMSX) elimination route. By attaching TMS groups to the nitrogen atoms

of 4 we hoped to eliminate TMSX from metal halide precursors which are commercially

available and offer abundant variations with respect to choice of transition metal and oxidation

state. The first step in creating TMS derivatives of 4 requires the synthesis of a dimagnesio salt,









which led to an interesting observation. When 4 is treated with MeMgCl and after removal of

THF the chelated magnesium product [3,5 -CF3N"C"N]Mg(THF)2 (10) was extracted with

pentane and single crystals were obtained (Scheme 2-4). This N,N-chelated product is a side

product and is only obtained in a minimal yield, however, enough was isolated to enable both

low temperature 'H NMR spectroscopy and X-ray structure determination.

The X-ray structure (Figure 2-4) obtained at 173 K indicates that the magnesium is

oriented such that the ipso-aryl C-H bond is positioned directly over the metal center. The

tetrahedral coordination sphere is comprised of the two amides from the ligand and two oxygen

atoms from coordinated THF molecules. After chelation of the amides it is apparent that the

ligand is in the correct conformation for C-H activation by a metal. This result provides insight

into a potential metallation route in which the arms first attach and then the backbone C-H bond

is activated. While this confirms pendant arm chelation as a possible route to installing

trianionic ligands on target metals the magnesium in this complex is unable to accomplish this as

it is lacks an accessible higher oxidation state. In the 1H NMR spectrum the protons in the

coordinated THF molecules are shifted 0.5 ppm upfield. The methylene and coordinated THF

protons are fluxional on the NMR time scale resulting in their appearance as broad peaks at

ambient temperature. As the temperature is reduced to -75 OC the protons in the ligand

methylene groups begin to resolve away from the THF protons. Unfortunately the low yield of

10 prevented further investigation and the synthesis of the [3,5-CF3N"C"N]TMS2H (11) was

conducted by in situ preparation of a dimagnesio salt.

Synthesis and Characterization of [3,5-CF3NCCCN]TMS2H ()

The N,N-TMS derivative 11 was formed by treating 4 with 2.1 equiv of methyl Grignard,

followed by addition of 3 equiv of TMSC1. 11 is obtained as a white crystalline solid in 74%









yield (Scheme 2-5). The 1H NMR spectrum of 11 revealed the expected signals for the

methylene groups and the singlet from the ortho-aryl protons formerly at 6.48 ppm for ligand 4

shifted to 7.35 ppm. The prominent feature of the spectra is the singlet at 0.00 ppm which is

assigned to the six methyl groups from two trimethylsilyls. Integration of the singlet from the

TMS groups only indicates fifteen protons, rather than the expected eighteen. This can be

attributed to a difference in relaxation times for these protons though they were not determined

and the identity of 11 was confirmed by additional means. 19F NMR shows only one sharp

singlet at -63.32, indicating only one compound is formed and a 13C NMR spectrum indicated

the presence of twelve peaks, the largest attributed to the SiMe3 carbons at 0.75 ppm.

Ligand 11 was treated with TiCl4, ZrF4, TaFS, Zrl4, and MoClS in refluxing toluene or

xylenes for 12-24 hr periods. The 1H NMR spectrum of the ZrF4 reaction mixture showed only

11 even after 20 hrs in refluxing xylenes, indicative of the thermal stability of the ligand.

Reactions with TaFS, Zrl4, and MoClS gave products whose NMR spectra were consistent with

the parent ligand 4. This occurred even after care was taken to silylate all glass surfaces to

reduce the likelihood that protons were coming from the glassware. The presence of TMSI and

TMSCl in the 1H NMR spectra indicated that the ligand was reacting with metal halides, but was

not anchoring via C-H bond activation of the backbone. Only reactions with TiCl4 showed the

presence of a product (in the 1H NMR spectra up to 33%). The 1H NMR spectra showed new

peaks attributed to the two pairs of methylene protons at 3.72 and 2.55 ppm. The position of

these suggests a new product was formed with titanium. The product was never isolated and

pale yellow crystals were grown but deteriorated before X-ray analysis could be conducted.









Conclusions

Metallation attempts with ligand 4 revealed two problems. Lack of rigidity promotes

dimerization and sterics force the two pendant arms apart. This is further complicated by slow

reactivity in aminolysis reactions. Without a driving force to chelate a single metal or without

the pendant arms being forced together, ligand 4 has an affinity for dimerization. The TMS-

halide elimination metallation route has similar drawbacks. While metal chelated pincers are

very robust, the high temperatures used to promote reactions of 11 with metal halides ultimately

lead to N-M bond protonation. While this remains a viable route to metallation, it will require

additional modification of the NCN ligand.

Experimental

General Considerations

Unless specified otherwise, all manipulations were performed under an inert atmosphere

using standard Schlenk or glovebox techniques. Pentane, hexanes, toluene, diethyl ether,

tetrahydrofuran, and 1,2-dimethoxyethane were dried using a GlassContour drying column.

C6D6 and toluene-ds (Cambridge Isotopes) were dried over sodium-benzophenone ketyl,

distilled or vacuum transferred and stored over 4 A+ molecular sieves. THF-ds (Cambridge

Isotopes) was stored over 4 A+ sieves and used without further purification. Sublimed Zr(NMe2)4

was purchased from Strem Chemicals and used without further purification. LiAlH4 (95%), m-

xylylenedicyanide (99%), and 2-bromomesitylene (99%), were purchased from Acros and used

as received. Pd2(db a)3, 3,5 -bi s(trifluoromethyl)b romob enzene, MeMgCl (3.0 M in THF), and

chlorotrimethylsilane (97%) were purchased from Aldrich and used as received. rac-BINAP

was purchased from Fluka and used as received. Mo(NMe2)4 WaS synthesized according to the

procedure from Chisholm et al.33









NMR spectra were obtained on Gemini (300 MHz), VXR (300 MHz), or Mercury (300

MHz) spectrometers. Chemical shifts are reported in 6 (ppm). For 1H and 13C NMR spectra, the

residual protio or carbon solvent peak were referenced as an internal reference. GC/MS spectra

were recorded on an Agilent 6210 TOF-MS instrument. C, H, and N elemental analysis were

determined by Robertson Microlit Laboratories Inc. and Complete Analysis Laboratories.

Synthesis of 2,2'-(1,3-phenylene)diethanamine (2)

An alternative synthesis of 2 was performed.34 Under argon flow diethyl ether (500 mL)

was added to LiAlH4 (60 g, 12.7 equiv, 1.58 mmol) in a 1000 mL three-neck flask fitted with a

reflux condenser, a 500 mL dropping funnel and a stirbar. To the dropping funnel was added m-

xylylene dicyanide (1) (19.4 g, 0.124 mol) in diethyl ether (300 mL). The m-xylylene dicyanide

solution was added dropwise under static argon over a period of 2 h with vigorous stirring and

then refluxed for 48 h. The resulting green suspension was cooled to 0 OC and then water (100

mL) was added dropwise through the dropping funnel, followed by a 15% by wt. solution of

NaOH (100 mL). Extra diethyl ether was added periodically. An additional 30 mL of water was

added to produce a free-flowing white suspension. Compound 2 was extracted from the white

suspension with diethyl ether (6 x 150 mL) and each portion was dried over Na2SO4 then

condensed in vacuo and combined. The transparent yellow oil was purified by distillation at 170

oC @ 20 mTorr. Yield 6.0 g (0.036 mol, 39.0%). 1H NMR (300 MHz, C6D6, 6): 7.15 (t, J= 7.30

Hz, 1H, Ar H), 6.99 (s, 1H, Ar H), 6.97 (s, 2H, Ar H), 2.88 (t, J= 6.86 Hz, 4H, -NH2-CH2), 2.65

(t, J= 6.86 Hz, 4H, -CH2-Ar), 1.01 (br. s, 4H, NH2).

Synthesis ofN,N'1-(2,2'-(1,3-phenylene)bis(ethane-1dil)s(46trmhynlne (3)

To a 100 mL round bottom flask charged with a stir bar and toluene (50 mL) were added 2

(0.920 g, 5.61 mmol), 2-bromomesitylene (2.230 g, 2 equiv, 11.22 mmol), Pd2(dba)3 (0.080 g,









0.5%, 0.087 mmol), rac-BINAP (0.140 g, 1.5%, 0.219 mmol), and NaOtBu (1.617 g, 16.83

mmol). After refluxing for 72 h under argon the solution was filtered through celite while hot

and the remaining toluene was removed in vacuo. Nonvolatile products were then taken up in

hot pentanes and filtered again through celite. The final product was produced as a light red oil

after volatiles were removed in vacuo. Yield 1.36 g (3.4 mmol, 61%). 1H NMR (300 MHz,

C6D6, 6): 7.14 (s, 1H, ipso-Ar H), 7.08 (t, J= 7.61 Hz, 1H, Ar H), 6.91 (d, J= 5.97 Hz, 2H, Ar

H), 6.75 (s, 4H, Ar H), 3.08 (dt, J= 6.86 Hz, J= 0.86 Hz, 4H, N-CH2-), 2.80 (t, J= 7.01 Hz, 2H,

NH), 2.63 (t, J= 6.86 Hz, 4H, Ar-CH2-), 2.15 (s, 6H, Ar-4-CH3), 2.06 (s, 12H, Ar-2,6-CH3).

Synthesis of N,N'1-(2,2'-(1 ,3-phenylene)bis(ethane-2,1l-diyl))bis(3,5-
bis(trifluoromethyl)aniline) (4)

To a 100 mL round bottom flask charged with a stir bar and toluene (50 mL) were added

2 ( 1.500 g, 9. 15 mm ol), 3,5 -b is(tri fluorom ethyl)b rom ob enzene (5.3 70 g, 2 equiv, 1 8.3 mm ol),

Pd2(dba)3 (0.130 g, 0.5%, 0.142 mmol), rac-BINAP (0.228 g, 1.5%, 0.357 mmol), and NaOtBu

(2.637 g, 27.5 mmol). After refluxing for 72 h under argon the solution was filtered through

celite while hot and the remaining toluene was removed in vacuo. Nonvolatile products were

then taken up in hot pentanes and filtered through celite again. The final product was

recrystallized two times in pentane at -20 OC. Yield 2.1 g (3.57 mmol, 39.0%). 1H NMR (300

MHz, C6D6, 6): 7.22 (s, 2H, Ar H), 7. 11 (t, J= 7.64 Hz, 1H, Ar H), 6.81 (dd, J= 7.64, 1.70 Hz,

2H, Ar H), 6.72 (s, 1H, Ar H), 6.48 (s, 4H, Ar H), 3.13 (t, J= 5.52 Hz, 2H, NH), 2.73 (dt, J =

6.94 Hz, 4H, N\H-CH2-), 2.38 (t, J= 6.94 Hz, 4H, -CH2-Ar). 13 glH} NMR (128.39 Hz, C6D6,

6): 35.35 (s, -CH2-Ar), 44.62 (s, -HN-CH2-), 110.38 (s, aromatic), 112.27 (s, aromatic), 122.85

(s, aromatic), 126.47 (s, aromatic), 127.60 (s, aromatic), 129.71 (s, aromatic), 132.97 (q, J=

32.74 Hz, -CF3), 139.76 (s, ArC-CH2-), 149.16 (s, ArC-NH-). HRMS calculated (found) for

C26H20Fl2N2 (M+H ) 589.1508 (589.1537).









Synthesis of [p-(3,5-CF3NCCCN)Zr(NMe2)3 NMe2 2 (7)

A solution of Zr(NMe2)4 (45 mg, 0. 170 mmol) in toluene (1 mL) was added to 4 (100 mg,

0.170 mmol) in toluene (1 mL) at -35 OC with stirring. After warming to ambient temperature

and stirring for 3 h, volatiles from the resulting brown solution were removed in vacuo. The

product was recrystallized from concentrated solutions of 7 in toluene over a period of 7 days.

1H NMR (300 MHz, THF-Ds, 6): 7.39-6.98 (m, 18H (11H), Ar H), 3.78 (t, J= 8.49 Hz, 4H, N-

CH2-), 3.13 (s, 12H, -N(CH3)2), 2.77 (t, J= 7.64 Hz, 4H, Ar-CH2-), 2.31 (s, 6H, HN(CH3)2), 2.28

(s, 1H, HN(CH3)2). 13 g lH} NMR (67.57 Hz, THF-Ds, 6): 21.52 (s, HN(CH3)2), 35.24 (s, -N-

CH2-), 36.07 (s, -N-CH2-), 39.36 (s, N(CH3)2), 43.04 (s, N(CH3)2), 45.57 (s, Ar-CH2-), 50.02 (s,

Ar-CH2-), 109.57 (s, aromatic), 112.22 (s, aromatic), 115.75 (s, aromatic), 123.38 (s, aromatic),

126.08 (s, aromatic), 127.33 (s, aromatic), 128.95 (s, aromatic), 129.72 (s, aromatic), 133.30 (q, J

= 32.0 Hz, CF3), 141.02 (s, aromatic), 155.53 (s, aromatic). Anal. Called for C .4H 4F 4Nlor2 (2

C6D6) C, 50.95; H, 4.13; N, 7.82. Found: C, 49.28; H, 4.50; N, 5.83.

Synthesis of pu-(3,5-CF3NCCCcN)[Mo(NMe2)3 2 (s)

To a 50 mL sealed ampule charged with a stir bar and toluene (25 mL) were added [3,5-

CF3NcCCN]H3 (4) (250 mg, 0.425 mmol), and Mo(NMe2)4 (350 mg, 1.275 mmol). After heating

to 40 oC for 4 d all volatiles were removed in vacuo. The remaining purple solid was gently

heated in vacuo to 50 OC for 48 h to sublime the unreacted Mo(NMe2)4. 1H NMR (300 MHz,

C6D6, 6): 7.34 (br. s, 1H, ipso-Ar H), 7. 14 (br. s, 2H, Ar H), 7. 11 (br. s, 2H, Ar H), 7.05 (br. s,

2H, Ar H), 7.03 (br. s, 1H, Ar H), 7.01 (br. s, 1H, Ar H), 3.73 (t, J= 8.35 Hz, 4H, N-CH2-), 3.08

(br. s, 36H, N(CH3)2), 2.84 (t, J= 7.76 Hz, 4H, Ar-CH2-). 13 glH} NMR (67.57 Hz, C6D6

128.39, 6): 37.58 (s, -CH2-Ar), 50.50 (s, N(CH3)3), 56.52 (s, N-CH2-), 110.91 (s, aromatic),









116.48 (s, aromatic), 126.91 (s, aromatic), 127.33 (s, aromatic), 129.59 (s, aromatic), 129.76 (s,

aromatic), 132.88 (q, J= 32.06 Hz, CF3), 140.82 (s, aromatic), 156.39 (s, aromatic).

Synthesis of [p-(3,5-CF3NCCCcN]HMg(THF)2 (10)

MeMgCl (1.30 mL, 3.0 M, 3.9 mmol) in THF (2 mL) was added dropwise to [3,5-CF3-

NcCCN]H3 (4) (1.0g, 1.70 mmol) in THF (2 mL) with a magnetic stirbar at -35 oC. After 3 h

volatiles were removed in vacuo and a dark yellow powder remained. Pentanes (3 mL) were

added to the powder and stirred for 12 h. The suspension was filtered and white needle crystals

were grown from a concentrated solution of the filtrate at -35 OC over a period of 48 h. Enough

product was produced for x-ray analysis and 1H NMR but not for EA or 13 1lH} NMR

spectroscopy. 1H NMR (300 MHz, Tol-Ds, -75 OC 6): 7.25 (s, 2H, Ar H), 7.16 (s, 2H, Ar H),

7. 13 (s, 1H, Ar H), 6.91 (s, 2H, Ar H), 6.77 (t, J= 6.74 Hz, 1H, Ar H), 6.55 (br. s, 2H, Ar H),

3.62 (d, J= 12.31 Hz, 1H, O-CH2-), 3.23 (br. s, 1H, O-CH2-), 3.07 (br. s, 2H, O-CH2-), 2.95 (br.

s, 4H, N-CH2-), 2.28 (br. s, 2H, O-CH2-), 2.14 (m (9), 2H, O-CH2-), 0.98 (br. s, 8H, -CH2-CH2-),

0.92 (t, J= 7.33 Hz, 4H, Ar-CH2@-)

Synthesis of [3,5-CF3NCCCN]H(SiMe3)2 (1)

To a solution of THF (2 mL) containing 4 (1.01 g, 1.72 mmol) and a stirbar, MeMgCl

(1.3 mL 3 M, 3.25 mmol) in THF (2 mL) was added dropwise at -35 oC. The solution was

stirred at ambient temperature for 3 h. Chlorotrimethylsilane (610 mg, 5.65 mmol) of was added

at -35 oC. The solution was kept at -35 OC for 1 h then stirred at ambient temperature for 15 h.

1,4-dioxane (2 mL) was then added causing precipitation ofMgCl2. The solution was filtered

and volatiles were removed in vacuo causing crystallization of the product. Yield 93 1 mg (1.27

mmol, 73.8%). 1H NMR (300 MHz, C6D6, 6): 7.40 (s, 2H, Ar H), 7.35 (s, 4H, Ar H), 7.02 (t, J =

7.61 Hz, 1H, Ar H), 6.77 (dd, J= 1.64, 7.61 Hz, 2H, Ar H), 6.68 (s, 1H, Ar H), 3.23 (t, J= 7.46









Hz, 4H, N-CH2-), 2.48 (t, J= 7.31 Hz, 4H, Ar-CH2-), 0.00 (s, 18H (15H observed), SiMe3).

13 1lH} NMR (128.39 C6D6, 6): 0.74 (s, Si(CH3)3), 35.60 (s, -CH2-Ar), 49.00 (s, -CH2-N),

112.34 (s, aromatic), 118.74 (s, aromatic), 120.81 (s, aromatic), 122.90(s, aromatic), 129.57 (s,

aromatic), 129.57 (s, aromatic), 129.91 (s, aromatic), 132.75 (q, J= 32.23 Hz, CF3), 140.07 (s,
aromatic), 150.75 (s, aromatic). 19F( H} NMR (C6D6, 6): -63.232 (s, CF3) Anal. Cald for


C32H36Fl2N2Si2: C, 52.45; H, 4.95; N, 3.82. Found: C, 52.470; H,4.816; N,3.689.

X-ray Experimental Details For [3,5-CF3-NCCCN]H3 (4)

Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD

area detector and a graphite monochromator utilizing MoKa radiation (h = 0.71073 A+). Cell

parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was

collected using the co-scan method (0.30 frame width). The first 50 frames were re-measured at

the end of data collection to monitor instrument and crystal stability (maximum correction on I

was < 1 %). Absorption corrections by integration were applied based on measured indexed

crystal faces.

The structure was solved by the Direct Methods in SHELXTL6, and refined using full-

matrix least squares. The non-H atoms were treated anisotropically, whereas the hydrogen atoms

were calculated in ideal positions and were riding on their respective carbon atoms. The

asymmetric unit consists of two chemically equivalent but crystallographically independent.

They differ by the orientations of the side aryl rings with respect to the central one. Out of the

eight CF3 groups, six of them are disordered and were refined in two parts each. A total of 890

parameters were refined in the Einal cycle of refinement using 10886 reflections with I > 20(I) to

yield R1 and wR2 of 6.33% and 13.87%, respectively. Refinement was done using F2









X-ray Experimental Details For pu-(2,6-iPrNCN) [Zr(NMe2)3 2 (6)

Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD

area detector and a graphite monochromator utilizing MoKa radiation (h = 0.71073 A+). Cell

parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was

collected using the co-scan method (0.30 frame width). The first 50 frames were re-measured at

the end of data collection to monitor instrument and crystal stability (maximum correction on I

was < 1 %). Absorption corrections by integration were applied based on measured indexed

crystal faces.

The structure was solved by the Direct Methods in SHELXTL6, and refined using full-

matrix least squares. The non-H atoms were treated anisotropically, whereas the hydrogen atoms

were calculated in ideal positions and were riding on their respective carbon atoms. A total of

507 parameters were refined in the final cycle of refinement using 10924 reflections with I >

20(I) to yield R1 and wR2 of 3.95% and 8.19%, respectively. Refinement was done using F2

X-ray Experimental Details For [CL-(3,5-CF3NCCCN)Zr(NMe2)3HNMe2] 2 (7)

Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD

area detector and a graphite monochromator utilizing MoKa radiation (h = 0.71073 A+). Cell

parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was

collected using the co-scan method (0.30 frame width). The first 50 frames were re-measured at

the end of data collection to monitor instrument and crystal stability (maximum correction on I

was < 1 %). Absorption corrections by integration were applied based on measured indexed

crystal faces.

The structure was solved by the Direct Methods in SHELXTL6, and refined using full-

matrix least squares. The non-H atoms were treated anisotropically, whereas the hydrogen atoms









were calculated in ideal positions and were riding on their respective carbon atoms. The

asymmetric unit consists of a half dimer and a benzene solvent molecule. The complex had all

four CF3 groups disordered and each set of three F atoms was refined in three positions with

their site occupation factors dependently refined to a total of onl. All F atoms were refined with

isotropic displacement parameters. A total of 543 parameters were refined in the final cycle of

refinement using 7414 reflections with I > 20(I) to yield R1 and wR2 of 5.37% and 13.33%,

respectively. Refinement was done using F2

The toluene molecule were disordered and could not be modeled properly, thus program

SQUEEZE, a part of the PLATON package of crystallographic software, was used to calculate

the solvent disorder area and remove its contribution to the overall intensity data.

X-ray Experimental Details for [p-(3,5-CF3NCCCN]HMg(THF)2 (10)

Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD

area detector and a graphite monochromator utilizing MoK, radiation (h = 0.71073 A+). Cell

parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was

collected using the co-scan method (0.30 frame width). The first 50 frames were re-measured at

the end of data collection to monitor instrument and crystal stability (maximum correction on I

was < 1 %). Absorption corrections by integration were applied based on measured indexed

crystal faces.

The structure was solved by the Direct Methods in SHELXTL6, and refined using full-

matrix least squares. The non-HI atoms were treated anisotropically, whereas the hydrogen atoms

were calculated in ideal positions and were riding on their respective carbon atoms. Two of the

four CF3 groups are disordered one in two part and the other in three parts. Their site occupation

factors were dependently refined and their displacement parameters were treated isotropically. A










total of 556 parameters were refined in the Einal cycle of refinement using 4126 reflections with I

> 20(I) to yield R1 and wR2 of 5.60% and 14.61%, respectively. Refinement was done using F2


/ \ H-N12eqtLiAlH4

--N


NH0.5 00 Pd2(dba) A N A


,NH2 H H


3, Ar = 2,4,6-MeC6H2
1 2
4, Ar = 3,5-CF3 6H3

Scheme 2-1. Synthesis of ArNcCcNH3 (where Ar = 2,4,6-MeC6H3 (3) and 3,5-CF3 6H3 (4)).


,Ar
/
H
N

N'Ar
5


Me2 N NMe2
M,~M2, r`z I~/F ZI',NIMe2
NMe2 NMe2





ArN N A
(Me2N)2Z --NHMe2 (Me2 )2Z --NHMe2

Ar/N 2~N'Ar


1 eq Zr(NMe2 4 >
toluene
20oC

Ar = 2,6-iP rC6H3


Ar'N NAr1 eqtZr(NMe2 4 >
H H 2 C


4 Ar = 3,5-CF3C6H3

Scheme 2-2. Synthesis of 6 and 7 (where Ar = 2,4- PrC6H3 (6) and 3,5-CF3 6H3 -7)










,Ar
H

H

5 Ar


1 eq Mo(NMe2 4
~~ No Reaction
tolue ne
110 oC
Ar = 2,6-iPrC6H3


Ar'N NAr


Ar\ ,Ar
H H


2.5 eq Mo(NMe2)4
toluene
40 oC

Ar = 3,5-CF3 6H3


Mo
Me2N NMeN,2


Me2N Meble


Scheme 2-3. Dramatic reactivity difference between ligands 4 and 5. Synthesis of the
molybdenum dinuclear species pu-(3, 5-CF3NcCcN)[Mo(NMe2>3 2 -s)


MgCl(THF)2
'A~r


Ar\- I~.~ ~-Ar21e.M~C, \H+
H H
-35 oC Ar

MgCl(THF)2
4 Ar = 3,5-CF3 6H3 9 Major Product


H NArTH

'THF
'Ar


10 Minor Product


Scheme 2-4. Synthesis of the dimagnesio salt [3,5-CF3NcCcN]H[MgCl(THF)2 2 (9) and the
minor impurity monomagnesio salt [pu-(3 ,5-CF3NcCcN]HMg(THF)2 (10).


~Siae 3



'R
SiMe3


Ar'N NA 2.x xM~eMgCI,23 eSC
H H


R = 3,5-CF3 6H3


Scheme 2-5. Synthesis of the bistrimethylsilyl species [3,5-CF3NcCcN]H(SiMe3)2 (11).









_:I1


N1l'


Fiue21 REPdarmo 3,-FN~NH () hra llpod r islyda h
50% prbblt ee. yrgnaosad orsalzdslvn oeue r

omtedfr lriy

















J


N2


N8



Figure 2-2. ORTEP diagram of (2,6-'Pr-NCN)[ZTr(NMe2 3 2 (6). Thermal ellipsoids are
displayed at the 50% probability level. Hydrogen atoms and cocrystallized solvent
molecules are omitted for clarity.
















Figre -3 OREP diga of-(,-F-c N)Z( e22227.Thr l
ellipsoid ar ipae tte5%poailt ee.Hdoe tm n
cocrstalize sovn mlcle r o itd o laiy

















Figre2-. RTP iara o [p(35-F3c~N]~gTH)2(10. hema elisodsar
dipae a h 0 poaiity lee.Hdoe tm ndccytlieovn
moleulesare mittd fo claity


















































































3.99
LI
**I' "'i"' 'li''i' nes u
2.(1 1.5 1 .D


: i g i i i i i g i i i i
6.5 6.0 5.5 5.0 4.5 4.0 3.5
Cherrilcal Sht't(ppril)


Figure 2-5. 1H NMR spectra of 2,2'-(1,3 -phenylene)diethanamine (2) in C6D6.


*


*
l l i n u i n a i l l * : i * *


73blsarilnE.ieBy


H2
-C- -N H2


NH2

NH2


2


H2
Ar--C -


--NH,


1.W*1.92
UI 5


I1 g1 1 1 l
7.0


4.20 4.2E*
I I.J


I II l lII
3.El 2.5

















































CH3














H2 H2
--C -NH Ar-C6


I II I I I I I I I I II I II II I I IIII I I II


ETIT.Iy Bda y E~p


1.243.43 3.711
U.. U I.I


I I I
7.0 6.5


4.301 2 EE 14 ZA
L.JUI


12.19
L.I


5.D d..5
clierrical s;htiltpprn]


4.D 3.5 3.D 2.5 2.D


Figure 2-6. 1H NMR spectra of [2,4,6-MeNcCcN]H3 (3) 111 C6D6.


N N
H H











CF3.Esp


F33 C3


H H


H2
Ar-C -


H2
--C -N)


1.05 D.93 3.92 1.93 4.DO1 392
LU.ILU IU I. U LJ ..
T.E 7. E.5 Ea 5. co 0 4 5 4.0 3.5 3.0 2.5 2.0
Cchmical shr~t ;prrfl

Figure 2-7. 1H NMR spectra of [3,5-CF3NcCcN]H3 (4) in C6D6












CF3_13 ers


144 13E 12B 120 112 13 46 6B 8G 72 64 56 4E AD 2
Ciembcaf Shrt(ppm)

Figure 2-8. 13 g lH} NMR spectrum of [3,5-CF3NcCcN]H3 (4) in C6D6*










c~zr 1ENn'R eBp


Ar, Ar

N N "

Ar 'A



Ar = 3,5-CFzC,H,


N N(CH3)2
(H2 )3 -rN
NH(CHz)2


IZJN~ N N(CHz)2

NH(CHz)2


H.


FC*


H2 -I H2
--C N I ~Ar--C --






15.16 4.D1 12.19 4.22 1.45
I.. J I.. L L.11
I ''''I I ''' lI ''' I' I I' '"I '"" ''I '"'' l I l II '''' I I '' ""' I' l l i l" l I I
7.5i 7.0 6.5i E. 5.5 6.0 4.E 4.0 3.5i 3.0 2.5
Chemical Shrt (ppm)

Figure 2-9. 'H NMR spectra of [pu-(3,5-CF3NcCcN)Zr(NMe2)3 8~2 2 (7) 111 C6D6.

















Ar'N NAr
I/ I"\T ~
!MeLN)2Zr--NHMe2 (Me2 )2Zr-NHMe2
ArN N'Ar



Ar = 3,5-CFC H,






























P I I l l I I I l i l l H ll i l I H l l I I l "I l l I I l "
12 14 13 1Bh; 12 1 % 9 S E 7 4 5 8 4 2
Chilia Sht ppil

Figur 2-0 3 1}N Rsetu f[-35C3cc)rN e) 22()i H -8


ZrInrelar13CNMR.eap



















































i-i^ --rl--r y -- I -rC---r- --1 --1 1- -r -x.l_. -.~


1.57 6.50 3.71
LJ LJ. I. U
7.01 6.5 lj.O 5.5 5.D 4.5 4.0 3.5
Chainica ShR(Wtn;pri
Figure 2-11i. 1H N\MR spectra of pu-(3,5-CF3NcCcN)[Mo(NTMe2)3 2 (8) 111 C6D6


CF3lbiNMe2 Yac :43Prs AC.elip


Ar'NI N, Ar
M~o Mo.
Me2NN~Ne 2 Me2 M heNMeg

Ar = 3,5-CF3 6H3


N
M~o
(H3C)2 1NCH3)2


H2

~-~I~


L. U
3.0


_J~











































































80 72 64 SE 48 4D


Figure 2-12. 13C t1H} N\MR spectrum of pu-(3 ,5-CF3NcCcN)[Mo(NMe2>3] 2(s) 11 C6D6.


III


1?52 144 136 125


CF3WG2_C13~esp


I~

Mvo M~o.
Me2N 2le Me2 `;e:NM 2


Ar = 3,5-CF3CsH3


1201 112 104 96 85
CliEmklat ShRtppm)]





































































3 75 515


F figure 2 13. 1H NMR sp ectra of [ 3,5 -CF 3NcCcN]HMg(THF)2 (10) i n Tol-d8 @ 75 o C.


-rr


T


CF3WI_75C.esp


H2
C
SCH2


NO6

il,CH2
H,


10
Ar = 3,5-CFCBH3














I.



I I











r- I| ,


Ar
H2CN ,O(CH2)2
Mg
H2CN 11(CH2)2


D EG ES4 1.462.82 2.62 2.27 3.95

7 ~ 7.11 SXI 5re cill 4 I 0.10 3.5 3|


3.15 2











NCN-CF3-2TMS 1H.elip


N


HC CH3


Ar = 3,5-CF3 6 3


3.6B; 1.16 D.B1 3.97 4.DO1 15.25

7.5 7.10 6.5 6.0 5.5 5.0 4.5 4.a 3.5 3.10 2.5 2.0 1.5 1.0 D.5 D
Chernkcal Shrt(pl='Ii

Figure 2-14. 'H NMR spectra of [3,5-CF3NcCcN]H(SiMe3)2 (11) 111 C6D6








































































152 144 136 120 120 112 134 95 6 88 S 72 El EG 46 40 32 24. 15 6
Chemical Shrt~pprrf

Figure 2-15. 13 ~1H} NMR spectrum of [3,5-CF3NcCcN]H(SiMe3)2 (11) 111 C6D6.


CF3-2TMs 13C.elip


Ar = 3,5-CFC,H,









































































20 0 -20 -40 -1.3 -I -100 -12 -1401 -16D -100 -220 -220
Chefrikcal Shrt? pprn

Figure 2-16. 19F NMR spectrum of [3,5-CF3NcCcN]H(SiMe3)2 (11) 111 C6D6-


CF3-2 MS 19F "






f-r





Ar = 3,5-CF3 6 3











Table 2-1. Selected angles and bond lengths for crystal structures 6, 7, and 10

(2,6-'Pr-NCN)[Zr(NMe2) 3 2~~~C)z(Mi2 p 3,5-CF3-CC)Z(~22H~ 21 (7 F13,c cN]HMg(THF)2
(6) N)[r(Ne2)2 62)2 )(10)
Bond Lengths (A+)
Zr-N 1 2.137(2) Zr-N4 2.036(3) Mg-O2 2.0140(18)
Zr-N2 2.212(2) Zr-N5 2.037(3) Mg-N 1 2.019(2)
Zr-N4 2.036(3) Zr-N1 2.137(2) Mg-N2 2.026(2)
Zr-N5 2.037(3) Zr-N2 2.212(2) Mg-0 1 2.0491(18)
Zr-N3 2.461(3) Zr-N3 2.461(3)
Zr-N6 2.046(3)
Zr-N7 2.030(3)
Zr-N8 2.034(3)
Bond Angles (deg)
N4-Zrl-N5 110.96(10) N4-Zr-N5 114.44(11) 02-Mg-N1 110.69(8)
N4-Zrl-N3 105.44(10) N4-Zr-N1 122.10(10) 02-Mg-N2 103.98(8)
N5-Zrl-N3 107.72(11) N5-Zr-N1 121.45(10) N1-Mg-N2 130.58(9)
N4-Zrl-N1 108.41(10) N4-Zr-N2' 96.60(10) 02-Mg-01 100.77(8)
N5-Zrl-N1 114.12(10) N5-Zr-N2' 95.28(10) N1-Mg-01 103.00(8)
N3 -Zrl-N1 109.82(10) N1-Zr-N2' 92.44(9) N2-Mg-01 103.86(8)
N7-Zr2-N8 108.84(11) N4-Zr-N3 85.90(11)
N7-Zr2-N6 105.30(11) N5-Zr-N3 88.61(11)
N8-Zr2-N6 108.31(11) N1-Zr-N3 81.62(10)
N7-Zr2-N2 114.06(10) N2-Zr-N3' 174.00(10)
N8-Zr2-N2 108.74(10)
N6-Zr2-N2 111.40(10)











Table 2-2. Crystal data, structure solution and refinement for [3,5-CF3NcCcN]H3 (4)
identification code (acO4)
empirical formula C26H20Fl2N2
formula weight 588.44
T (K) 173(2)
it (A) 0.71073
crystal system Triclinic
space groupP-
a (A+) 11.9159(14)
b (A+) 14.003(2)
c (A) 16.6156(18)
a (deg) 75.343(2)
P (deg) 71.727(2)
r(deg) 74.212(2)
V (A3) 2490.3(5)
Z 4

Peld(gmabs coeff (mm ) 015
F(000) 1192
crystal size (mm3) 0.11 x 0.08 x 0.05
8 range for data collection 1.31 to 22.50
limiting indices -11 no. of refns called 10886
no. of ind reflns (Rint) 6488 [R(int) = 0.1286]
completeness to 0= 22.500 99.8 %
absorption corr Integration
refinement method Full-matrix least-squares on F2
data / restraints / parameters 6488 / 0/890
GOFe on F2 0.896
R1,a avR2b [I > 20] 0.0633, 0.1387 [3149]
R1,a lR2b (all data) 0.1350, 0.1701
largest diff. peak and hole 0.310 and -0.263 e.A-3
R1 = C(||Fo| |Fc||)/ I|Fo|, wR2 = [C[w(Fo2 Fc2)2] / C[w(Fo2)2 1/2, S = [C[w(Fo2 Fc2)23
(n-p)]1/2 w= 1/[o2(Fo2)+(m~p)2+n~p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants.









Table 2-3. Crystal data and structure refinement for pu-(2,6-'PrNCN)[Zr(NMe2)3 2 (6)
identification code (ky l 3)
empirical formula C44H78NsZr2
formula weight 901.58
T (K) 173(2)
it (A) 0.71073
crystal system Monoclinic
space group P21/n
a(A) 9.5540(4)
b (A+) 19.4781(9)
c (A) 26.2784(12)
a (deg) 90
fl (deg) 98.343(1)
7(deg) 90
V (A3) 4838.5(4)
Z 4
Pcaled (Mg mm-3) 1.238
abs coeff (mm ) 0.467
F(000) 1912
crystal size (mm ) 0. 18 x 0. 10 x 0.09
B range for data collection 1.57 to 27.500
limiting indices -6 no. of refns called 30297
no. of ind reflns (Rint) 10924 [R(int) = 0.0661]
completeness to 8= 22.500 98.3 %
absorption corr Integration
refinement method Full-matrix least-squares on F2
data / restraints / parameters 10924 / 0/507
GOFe on F2 0.854
R1,a avR2b [I > 20] 0.0395, 0.0819 [5881]
R1,a lR2b (all data) 0.0884, 0.0879
largest diff. peak and hole 0.593 and -0.778 e.A+
R1 = C(||Fo| |Fc||)/ I|Fo| wR2 = [C[w(Fo2 Fc2)2] / C[w(Fo2)2 11/2 S = [C[w(Fo2
Fc:2)2] / (n-p)]1/2 w= 1/[o2(Fo2)+(m*p)2+n~p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are
constants .









Table 2-4. Crystal data and structure refinement for [pu-(3,5-CF3NcCcN)Zr(NMe2)3 8e22 27
identification code (acO3)
empirical formula C76 H186 F24 N1o Zr2
formula weight 1777.99
T (K) 173(2)
At (A) 0.71073
crystal system Triclinic
space group P-1
a(A) 9.1226(5)
b (A+) 12.3882(7)
c (A) 18.5955(10)
a (deg) 77.615(1)
fl(deg) 79.183(1)
y(dee) 88.269(1)
V (A ) 2016.04(19)
Z 1
Pcaled (Mg mm-3) 1.464
abs coeff (mm ) 0.362
F(000) 908
crystal size (mm ) 0. 19 x 0. 19 x 0.06
B range for data collection 1.68 to 27.500
limiting indices -11 no. of reflns called 13079
no. of ind reflns (Rint) 8784 [R(int) = 0.0386]
completeness to 0= 22.500 94.9 %
absorption corr Integration
refinement method Full-matrix least-squares on F2
data / restraints / parameters 8784/ 4 /543
GOFe on F2 1.048
R1,a avR2b [I > 20] 0.0537, 0.1333 [7414]
R1,a lR2b (all data) 0.0638, 0.1398
largest diff. peak and hole 0.902 and -0.778 e.A+
R1 = C(||Fo| |Fc||)/ I|Fo|, wR2 = [C[w(Fo2 Fc2)2] / C[w(Fo2)2 1/2, S = [C[w(Fo2 Fc2)23
(n-p)]1/2 w= 1/[o2(Fo2)+(m~p)2+n~p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants.









Table 2-5. Crystal data and structure refinement for [pu-(3 ,5-CF3NcCcN]HMg(THF)2 (10)
identification code (acl1)
empirical formula C39H46F l2MgN202
formula weight 827.09
T (K) 173(2)
it (A) 0.71073
crystal system Monoclinic
space group P21/c
a (A+) 17.9480(12)
b (A+) 9.5720(7)
c (A) 24.8666(17)
a (deg) 90
P (deg) 110.180(1)
r (deg) 90
V (A3) 4009.8(5)
Z 4
Peld(gmabs coeff (mm ) 013
F(000) 1720
crystal size (mm3) 0.19 x 0.15 x 0.08
8 range for data collection 1.74 to 27.500
limiting indices -23 no. of refns called 26429
no. of ind reflns (Rint) 9163 [R(int) = 0.081 1]
completeness to 0= 22.500 99.4 %
absorption corr Integration
refinement method Full-matrix least-squares on F2
data / restraints / parameters 9163/ 1 /556
GOFe on F2 0.862
R1,a avR2b [I > 20] 0.0560, 0.1461 [4126]
R1,a aR2b (all data) 0.1284, 0.1636
largest diff. peak and hole 0.416 and -0.317 e.A-3
R1 = C(||Fo| |Fc||)/ I|Fo|, wR2 = [C[w(Fo2 Fc2)2] / C[w(Fo2)2 1/2, S = [C[w(Fo2 Fc2)23
(n-p)]1/2 w= 1/[o2(Fo2)+(m~p)2+n~p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants.









CHAPTER 3
SYNTHESIS AND REACTIVITY OF
TERPHENYL OCO3- PINCER COMPLEXES

Synthesis and Characterization of Terphenyl [tBuOCO]H3 (17)

Alkoxides react readily with metal amides, owing to the greater affinity of early transition

metals for oxygen than for nitrogen.35,36 Thus, an OCO3- pinCOT format (17) should effect an

increase in reactivity and stability with early transition metals. The alkyl groups must be of

sufficient size to prevent metal-metal bonds from forming as well as imparting protection to the

active site during reactions.37 The terphenyl framework also imparts greater rigidity to the pincer

backbone over the previous NcCcN design.

The synthesis of the terphenyl OCO ligand 17 is a five step sequence (Scheme 3-1)

starting with selective ortho-bromination of 2-tert-butylphenol (12) to give bromophenol 13.

Phenol 13 is then masked as its methyl ether, and the Grignard derivative of 14 is generated by

treatment with magnesium metal. Dibromoiodide 15 is easily made from 2,6-dibromoaniline via

diazotization, and is alkylated with 14. The bismethyl ether 16 is then deprotected by treatment

with boron tribromide. Purification by flash column chromatography- affords diol 17 as a white

solid in 21% yield from 12 (Scheme 3-1). The identity of 17 was verified by 1H NMR, 13C M

spectrometry and HRMS. The 1H NMR spectrum revealed the expected, singlet from two tert-

butyl groups that integrate to 18 protons at 1.44 ppm and two OH protons at 7.14 ppm. A 13C

NMR spectrum of 17 shows the 10 signals in the aromatic region with two signals at 35.541 and

30.279 ppm assigned to the carbons of the tBu groups. The calculated mass for 17 is 374.2240

amu and was experimentally found to be 374.2209 amu, confirming the identity of 17 as the

desired terphenyl diol.









Synthesis and Characterization of [tBuOCO]MoNMe2 6N~2)2 (18)

Diol 17 was treated with purple Mo(NMe2)4 in pentane at -35 OC (Scheme 3-2). As the

reaction warms an orange powder precipitates out of solution in 80% yield. Transparent orange

crystals were grown at -3 5 OC from DME over a period of two days.

The broadened peaks in the 1H NMR spectrum are characteristic of a paramagnetic

Mo(IV) bearing two unpaired electrons. The tBu groups are visible as a singlet that is shifted

from 1.44 ppm in the free ligand to 2.82 ppm upon coordination to Mo. Singlets at 1.73 and -

8.72 ppm are attributed to the pair of methyl groups on the coordinated amide. The methyl

protons on the amines appear as singlets at 3.45 and 1.98 ppm, with the NH proton at 3.26 ppm.

The ligand contributes 6e- to the metal and another 6e- are donated from the amide and two

amines. An additional 4e- occupy xn-bonding orbitals from the nitrogen and oxygen lone pairs.

Considering the additional 2e-from the metal, 18 is an 18e- complex. The structure of 18 was

determined by single crystal X-ray crystallography and the molecular structure is presented in

Figure 3-1. Clearly 17 is bound in a terdendate fashion to molybdenum with a dimethylamine in

the position trans to the ipso-carbon of the backbone, and the remaining axial positions are

occupied by coordinated dimethylamine and dimethylamide ligands. As expected with

molybdenum alkoxide compounds generated from Mo(NMe2)4, dimethylamine remains in the

coordination sphere.38 The amido and amine ligands are easily distinguished since Nl is trigonal

whereas N2 and N3 are pyramidal. In addition the M-N bond lengths are significantly different

(Table 3-1). The Mo-NMe2 ligand is twisted away from the N2-Mo-N3 plane by 350 to break

the otherwise perfect solid-state Cs symmetry. A space-filling model indicates the twist is due to

packing forces that place a DME solvent molecule atop the amido group. Considerable strain is

imparted to the pincer backbone and is attributable to congestion caused by the dimethylamine









ligand transrt~t~rt~t~rt~t~rt~ to C1. The N-Me groups are nearly parallel to the Ol- C1-O2 plane which forces

them into the tBu's of the pincer. As a result, the tBu groups are strained, creating 33o and 32o

torsion angles between the aryl backbone C2-C7 and C6-C 17 connections, respectively, and the

central ring is bent up by 300.

Synthesis and Characterization of [tBuOCO]MoCI (19)

To derivatize the complex such that it would be more amenable to salt metathesis, 18 was

treated with 3 equiv of lutidine hydrochloride in pentane.39 Three equivalents were required due

to the insolubility of lutidine hydrochloride in pentane (Scheme 3-3). This reaction results in

protonation of the remaining amide and installs a chloride transrt~t~rt~t~rt~t~rt~ to the M-C bond. The remaining

HCI salts were removed from the resulting red powder by filtration. The 1H NMR spectrum of

19 revealed broadened resonances indicative of a paramagnetic complex. The tBu protons of the

ligand appear at 1.37 ppm and the coordinated dimethyl amine protons have shifted upfield to -

2.02 ppm. Complex 19 was crystallized from benzene as single crystals up to 5 mm across,

which allowed for the structure to be determined by X-ray crystallography. X-ray structure

analysis shows the strain observed in the previous structure 18 is relieved, as the ligand has

acquired a 330 twist in the backbone along the Cll-Mo-C1 axis thus imparting 19 C2 symmetry

(Figure 3-2). The octahedral Mo(IV) center is coordinated by the pincer ligand, trans-dimethyl~t~t~t~t~t~t~

amines, and a chloride. The coordinated dimethylamines orient off axis by 570 and are rotated

88o with respect to each other, which, again, can be attributed to sterics. The 01-Mo-Ol1' angle

has decreased slightly from 166.450 in 18 to 165.320 (Table 3-1).

The chemistry of 19 was probed and it was determined that the dimethyl amines on 19 are

bound tightly and do not release under vacuum nor substitute with THF, DME or CO, even at









elevated temperatures (80 oC). In addition the complex is stable for short periods when exposed

to air.

Conclusions

Development of new trianionic pincer ligands is two-fold. While new ligand designs

need to be explored, successful routes to installing these new ligands on metals need to be

developed. Stepwise modifications of our original NCN format led to straightforward

metallation of molybdenum using an OCO pincer ligand. While the terdentate behavior of an

OCO ligand has now been established with molybdenum, metallation will require modification,

possibly to utilize molybdenum chlorides as reagents. Alternative metallation routes will avoid

coordinated dimethylamines which have proven difficult to remove and can impede further

reactivity. Formation of aryloxide alkali salts40 and aryl ethers41 are established and can provide

insight into alternative metallation routes with 17. Our previous work exploring reactivity of

early transition metals will also aid in this research. Established synthetic routes to our ligands

are easily modified to incorporate new designs quickly as needed. The research presented here

will provide a solid foundation for future development of trianionic pincer ligands.

Experimental

General Considerations

Unless specified otherwise, all manipulations were performed under an inert atmosphere

using standard Schlenk or glovebox techniques. Pentane, hexanes, toluene, diethyl ether,

tetrahydro-furan, and 1,2-dimethoxyethane were dried using a GlassContour drying column.

C6D6 and toluene-d8 (Cambridge Isotopes) were dried over sodium-benzophenone ketyl,

distilled or vacuum transferred and stored over 4 A+ molecular sieves. THF-d8 and acetone-d6

(Cambridge Isotopes) was stored over 4 A+ sieves and used without further purification.









NMR spectra were obtained on Gemini (300 MHz), VXR (300 MHz), or Mercury (300 MHz)

spectrometers. Chemical shifts are reported in 6 (ppm). For 1H and 13C NMR spectra, the

residual protio or carbon solvent peak were referenced as an internal reference. GC/MS spectra

were recorded on an Agilent 6210 TOF-MS instrument. C, H, and N elemental analysis were

determined by Robertson Microlit Laboratories Inc. and Complete Analysis Laboratories.

Synthesis of 2-bromo-6-tert-butylphenol (13)

This compound was made according to the procedure Zhang et al 42 Purification was

achieved by flash column chromatography (3:1 pentane;CHCl3) to give 13 as a clear colorless oil

in 81% yield. 1H NMR and 13C NMR were consistent with those previously reported.

Synthesis of 1-bromo-3-tert-butyl-2-methoxybenzene (14)

To a solution of 13 (6.06 g, 26 mmol) in DMF (30mL) was added K2CO3 (5.5 g, 1.5

equiv., 40 mmol) and Mel (2.5 mL, 1.5 equiv., 40 mmol). The resulting mixture was stirred at

ambient temperature for 16 h. Water was added, and the mixture was extracted (2X) with Et20.

The combined organic extracts were washed successively with water, saturated Na2S203 and

brine, dried over MgSO4, filtered and concentrated in vacuo to a yellow oil. Methyl ether 14 was

obtained by vacuum distillation (58-60 C @ 4 mTorr) as a white crystalline solid (5.76g. 90%

yield). 'H NMR (300 MHz, DMSO-d6) 6 7.47 (dd, 3J = 8. 1 Hz, 4J= 1.5 Hz, 1H), 7.29 (dd, 3J

8. 1 Hz, 4J= 1.5 Hz, 1H), 6.97 (dd, J= J= 8. 1 Hz, 1H), 3.83 (s, OCH3, 3H), 1.33 (s, tBu, 9H);

13C NMR DMSO-d6) 6 30.6 [C(CH3)3], 35.1 [C(CH3)], 61.1 (OCH3), 117.4 (CBr), 125.0

(=HC-CH-CBr), 126.6 (tBu-CH), 131.9 (=CH-CBr), 144.7 (C-tBu), 156.1 (COMe); HRMS (GC-

E1-C1) calc'd (found) for C11H1SBrO (M ) 242.0301 (242.0286).









Synthesis of 1,3-dibromo-2-iodobenzene (15)

This compound was made according to the procedure of Hart and coworkers.43 The

compound was recrystallized from isopropano before use. 1H and 13C NMR were consistent with

those previously reported.

Synthesis of 3,3"-di-tert-butyl-2,2"-dimethoxy-1,1' :3',1"-terphenyl (16)

This compound was made following the general procedure of Hart and coworkers.43 To a

solution of 2 (4.84 g, 3.5 equiv., 20 mmol) in dry THF (40 mL) was added Mg turnings (540 mg,

3.9 equiv., 22 mmol). The resulting mixture was heated to reflux for an additional 1 h. A

solution of 3 (2.06 g, 1 equiv., 5.7 mmol) in dry THF (20 mL) was added dropwise over 1 h to

the reaction mixture. The resulting mixture was heated at reflux for 16 h. The mixture was

cooled to room temperature, and was quenched with 6N HC1. The mixture was extracted with

Et20 (3 x 20 mL). The combined organix extracts were washed with saturated Na2S203 and

brine, dried over MgSO4, filtered and concentrated in vacuo to a brown oil. Terphenyl 16 was

obtained via flash column chromatography (8:1 hexanes:CHCl3) as a white solid (1.3 g, 57%

yield). 1H NMR (300 MHz, C6D6) 6: 13C N (6D6) 6 31.5 [C(CH3)3], 35.7 [C(CH3)3], 60.7

(OCH3), 124.2 (C 5,"), 127.0 (C 4',6' ), 128.4 (C 3,3" ), 129.3 (C 2,2" ), 130.5 (C 5~), 130.7 (C 6,6 )

136. 1 (C 1~"), 141.2 (C 11~3' ), 143.6 (C 3,3" ), 158.4 (C 2,2- ); HRMS (DIP-C1-MS) calc'd (found)

for C28H3402 (M ) 402.2553 (402.2536).

Synthesis of 3,3"-di-tert-butyl-1,1' :3',1"-terphenyl-2,2"-diol ([tBuOCO]H3) (17)

To a solution of 16 (1.3 g, 3.2 mmol) in CH2C 2 (20 mL) at 0 oC was added BBr3 (1.6 mL,

5 equiv., 16 mmol). The mixture was warmed slowly to room temperature over 6 h. MeOH was

added to quench the reaction, and the mixture was concentrated under reduced pressure. Diol 17

was obtained by flash column chromatography- of the residue (5:1 pentane:CHCl3) as a white









solid (600 mg, 50% yield). 1H NMR (300 MHz, acetone-ds) 6 7.58 (dd, J= J= 7.8 Hz, 1H, H2')

7.54 (dd, J = J = 1.8 Hz, 1H, H '), 7.38 (dd, 3J = 7.8 Hz, 4J = 1.8 Hz, H4''6'), 7.28 (dd, 3J = 8.1 Hz,

4J = 1.8 Hz, 2H), 7. 14 (s, 2 H, OH), 7.07 (dd, 3J = 8.1 Hz, 4J = 1.8 Hz, 2H), 6.89 (dd, J= J = 8. 1

Hz, 2H, H ,5), 1.44 (s, 18H, tBu); 13C NMR (C6D6) 6 30.3 [C(CH3)3], 35.5 [C(CH3)3], 121.0 (C

5,"), 127.7 (C 2' ), 128.8 (C 4',6' ), 129.0 (C 1~"), 129.1 (C 4,4- ), 130.7 (C 6,6- ), 131.5 (C ), 137.0

(C 1',3' ), 139.6 (C 3,3" ), 151.7 (C 2,2" ); HRMS (DIP-C1-MS) calc'd (found) for C26H3002 (M )

374.2240 (374.2209).

Synthesis of [tBuOCO]MoNMe2 6N~2)2 (8)

To a solution of [tBuOCO]H3 ligand (17) (500 mg, 1.34 mmol) in pentane (2 mL)

Mo(NMe2)4 (218mg, 1 equiv., 1.34 mmol) in pentane (2 mL) was added quickly at -3 5 oC. The

resulting brown slurry was stirred with a spatula until it was warmed to room temperature. The

orange precipitate was filtered off, washed with cold pentane and dried in vacuo. The product

([3,3"-di-tert-butyl-2,2"-di(hydroxy-O)-, 1':3', 1"-terphenyl-2'-yl-KC2'](N-

methylmethanaminato)bis(N-methylmethanamiemlbnu(V) (18) was recrystallized

from DME as dark orange crystals at -35 oC; Yield 642mg (1.07 mmol, 80%) 1H NMR (300

MHz, THF-Ds, 6): 9.61 (br. s, 2H, Ar H), 3.78 (s, 2H, Ar H), 3.45 (br. s, 3H, -NH(CH3)2), 3.26

(s, 1H, -NH(CH3)2), 3.17 (s, 1H, Ar H), 2.82 (s, 18H, -C(CH3)3), 2.14 (s, 2H, Ar Hs), 1.98 (br. s,

9H, -NH(CH3)2), 1.73 (s, 3H, -N(CH3)2), -8.72 (s, 3H, -N(CH3)2) 13 glH} NMR (67.57 Hz,

THF-Ds, 6): 29.76 (s, C, aromatic), 40.55 (s, CH, aromatic), 43.77 (s, -N(CH3)2), 47.28 (s, CH,

aromatic), 49.08 (s, -C(CH3)3), 58.31 (s, -C(CH3)3), 72.02 (s, CH, aromatic), 79.92 (br. s, C,

aromatic), 164 (br. s, C-O, aromatic). Anal. Called for C32H47MON302 C, 63.88; H, 7.87; N, 6.98.

Found C, 61.13; H, 6.90; N,3.63.









Synthesis of [tBuOCO]Mo(HNMe2)2C (9)

To a solution of [tBuOCO]Mo(NMe2)(HNMe2)2 (18) (250 mg, 0.415 mmol) in pentane (2

mL) was added lutidine HCI (180 mg, 3 equiv., 1.260 mmol). After vigorous stirring for 12 h

all volatiles were removed in vacuo and the remaining solid was dissolved in THF (2 mL).

Remaining lutidine HCI salts were filtered off with a medium porosity fritted funnel. Volatiles

from the filtrate were removed in vacuo and the remaining solid was triturated with pentane to

yield OCOtBuMo(HNMe2)Cl (19) as a dark red powder. The product was recrystallized from

benzene as dark red crystals; Yield 99 mg (0. 167 mmol, 40%) 1H N\MR (300 MHz, C6D6, 6):

29.40 (s, 2H, Ar H), 3.57 (br s, 1H, Ar H), 2.42 (s, 2H, Ar H), 1.55 (s, 2H, Ar H), 1.37 (s, 18H, -

C-(CH3)3), -1.40 (s, 3H, NH-(CH3)2), -2.02 (s, 3H, NH-(CH3)2), -2.25 (br. s, 9H, -NH-(CH3>2>, -

5.32 (s, 2H, Ar Hs). 13 g lH} ~NMR (67.57 Hz, THF-Ds, 6): 30.20 (s, -NH-(CH3)2), 41.24 (s, -

C(CH3)3), 44.95 (s, -C(CH3)3), 128.93 (s, CH, aromatic), 129.08 (s, CH, aromatic), 129.44 (s,

CH, aromatic), 163.11 (s, CH, aromatic), 173.11 (s, CH, aromatic). Anal. Called for

C42H41D12CIMON202 (2 C6D6) C, 66.22; H, 6.96; N,3.68. Found: C,66.03; H,7.05; N,3.72.

X-ray Experimental Details For [tBuOCO]MoNMe2 6N~2)2 (18)

Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD

area detector and a graphite monochromator utilizing MoK, radiation (h = 0.71073 A+). Cell

parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was

collected using the co-scan method (0.30 frame width). The first 50 frames were re-measured at

the end of data collection to monitor instrument and crystal stability (maximum correction on I

was < 1 %). Absorption corrections by integration were applied based on measured indexed

crystal faces.









The structure was solved by the Direct Methods in SHELXTL6, and refined using full-

matrix least squares. The non-HI atoms were treated anisotropically, whereas the hydrogen atoms

were calculated in ideal positions and were riding on their respective carbon atoms. In addition

to the complex, there is a dme molecule in the asymmetric unit. The protons, H1 and H12, on Nl

and N2 respectively, were obtained from a Difference Fourier map and refined without any

constraints. A total of 405 parameters were refined in the Einal cycle of refinement using 5629

reflections with I > 20(I) to yield R1 and wR2 of 4.77% and 9.57%, respectively. Refinement

was done using F2

X-ray Experimental Details For [tBuOCO]Mo(HNMe2)2C1 (9

Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD

area detector and a graphite monochromator utilizing MoK, radiation (h = 0.71073 A+). Cell

parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was

collected using the co-scan method (0.30 frame width). The first 50 frames were re-measured at

the end of data collection to monitor instrument and crystal stability (maximum correction on I

was < 1 %). Absorption corrections by integration were applied based on measured indexed

crystal faces.

The structure was solved by the Direct Methods in SHELXTL6, and refined using full-

matrix least squares. The non-HI atoms were treated anisotropically, whereas the hydrogen atoms

were calculated in ideal positions and were riding on their respective carbon atoms. The

asymmetric unit consists of a half complex and a benzene molecule of crystallization. The N

proton was located in a Difference Fourier map and refined freely. The complexes are located on

2-fold rotation axes of symmetry. A total of 223 parameters were refined in the final cycle of










refinement using 3320 reflections with I > 20(I) to yield R1 and wR2 of 2.63% and 7.71%,

respectively. Refinement was done using F2


1. Mg


lu B-r Mel, K2CO3~
DM F

13

M e2NBr
to luen e
-15 oC


tBu d


12


2. 15
THF, reflux



Br' yBr

15


16

BBr3
CH2C 2
0oOC


[t Bu OCO] H3
17


Scheme 3-1. Synthesis of [tBuOCO]H3 -1)







/ \ OH Mo(NMe2,4 / H
Mo-NH
OH ~pentane _O
-NHM e2


17 18

Scheme 3-2. Synthesis of [tBuOCO]MONMe2 6N~2> 2 (1-)














Mo-NH




18


2,6-lutidine'HCI
pentane
-NHMe2


Scheme 3-3. Synthesis of [tBu-TP]Mo(HNMe2)2C -1)


Figure 3-1. ORTEP diagram of [tBuOCO]MONMe2(HNMe2)2 (18). Thermal ellipsoids are
displayed at the 50% probability level. Hydrogen atoms and cocrystallized solvent
molecules are omitted for clarity.













01 ,
IC


,i ~ 01 "p l;
CI1 \ 0

IN1'



Figure 3-2. ORTEP diagram of [tBuOCO]Mo(HNMe2)2Cl (19). Thermal ellipsoids are
displayed at the 50% probability level. Hydrogen atoms and cocrystallized solvent
molecules are omitted for clarity.































































3.1 2.5 2.D 1.5


m


mku-114-ilica


C(CH,)3


Q(ICH 13






2. D 2.101.962.Di0
LJ UU UU LU L
7.5 7.0 E5 5. 5.E. 5.D 4.5 4.0 3.5
Cr ernicial Et.MIR upgil

Figure 3-3. IH NMR spectrum of [tBuOCO]H3 (17) in acetone-d6.


i


P






































BI
O
OE
0010
rlP1
f O
ON
m4rl
CY i:-









ndivr 4
rlg(D \O
O IDOI
01 oD I 'm
EP h 4 1 i" O
~INrl



ul,
,,
,,
,,
"P-nn
ar~r(
YI OPI I?

n, a
iorl~i u,













`I vr










160 140 120 100 80 60 QO




Figure 3-4. '3C NMR spectrum of ['BuOCO]H3 (17) in CsD6.




























































1.B3 1.30 3.B21.Er2 (1. 2.31

Cher~slncGI id Ippril
Figure 3-5. 'H NMR spectrum of [tBuOCO]MONMe2 6N~2)2 (18) in THF-ds.


j Ilmclr~l h ~d Ilh~lr~':~ nnF 6anw ~amlJC as ~RY~.esp


HNS

-N O b




18


C(CH,)z

















































rW'W~W~FIHKU


I I I I I I I I I I I I I I I I I I I I I I I Mil il""Hill""II"I"'llli111 11111111111111 111111111111 11111111 11111 l1111"I""I11111 "I11111111 l11
itiD 15;2 1 "4 184i 12B 120 112 1114 91 88 Bo 72 EA 65 48 4D 32 24
CI~rerrmSnl SId pp~n
Figure 3-6. 13C NMR spectrum of ['BuOCO]MONMe2 6N~2)2 (18) in THF-ds.


HN O
Mo-NH
- ObNV
/\l










18ry


uu~`J


c~lcrlrq
UIITT
crg~b
1" rrfl


T































































































Figure 3-7. 1H NMR spectrum of [tBuOCO]Mo(HNMe2)2C1 (19) 111 C6D6


11l111 "1"1 l""1"111i"1l "I"I111l "I ""'"H ll I'" ll "H i ll "I "M iil "I'P i li" H i I'
307 25 2E 24 22 20 la 16 14 12 10 8
CI'eirkralsnl Cppll)


16 '-.

I I


COCOkh3l lH.esp


0.QS0.97 127
J...I I. I I.. .J
"I""I'"Hl"I"" 'll""'""
6 4 2


12.5i5 2.23
I.l J..
11I" 1111" I111" 11111l"" 111" 1I"
0 -2 -4-6




























































































1E8 1601 152 144 13E 128 12D 112 1E4 963 Ba 8D 72 E 56 48 40 3224
CI'Enveal brrat if 11


Figure 3-8. 13C NMR spectrum of ['BuOCO]Mo(HNMe2)2Cl (19) in THF-ds.


E r. rr.
I-. I-.;.


OIC~BtEAollWCI T11F 13C.wyp









Table 3-1. Selected angles and bond
[tBuOCO]MONMe2(HNMe2)2 (8)
Bond Lengths (A+)
Mol-N1 1.928(3)
Mol-01 1.997(2)
Mol-O2 2.014(2)
Mol-C1 2.114(3)
Mol-N2 2.390(3)
Mol-N3 2.430(3)


lengths for crystal structures 18 and 19
[tBuOCO]Mo(HNMe2)2C (9)


Mol1-01
Mo l-C1
Mo l-N1
Mo l-Cll


1.9405(11)
2.120(2)
2.2245(16)
2.4829(6)




82.66(3)
83.24(5)
94.55(4)
97.34(3)
180.0
85.45(4)
128.73(10)
162.32(6)
170.90(8)


Bond Angles (deg)
N1-Mol-01
N1-Mol-O2
01-Mol-O2
N1-Mol-C1
01-Mol-C1
02-Mo l-C1
N1-Mol-N2
01-Mol-N2
C22-O2-Mol
02-Mol1-N2
C1-Mol-N2
N1-Mol-N3
01-Mol-N3
02-Mol1-N3
C1-Mol-N3
N2-Mol1-N3
C12-Ol-Mol


98.89(11)
94.58(10)
166.45(9)
98.88(12)
90.35(11)
89.05(11)
173.45(12)
83.68(10)
128.7(2)
82.77(9)
87.10(12)
92.35(12)
89.71(10)
88.23(10)
168.62(12)
81.60(12)
129.5(2)


01-Mol-C1
01-Mol-N1
C1-Mol-N1
01-Mol-Cll
C1-Mol-Cll
N1-Mol-Cll
C6-Ol-Mol
01-Mol-Ol'
N1-Mol-N1'









Table 3-2. Crystal data and structure refinement for [tBuOCO]MONMe2 6N~2)2 (8
identification code (ac20)
empirical formula C36H57MON304
formula weight 691.79
T (K) 173(2)
At (A) 0.71073
crystal system Triclinic
space group P-1
a(A) 8.5921(10)
b (A+) 11.8394(14)
c (A) 18.796(2)
a (deg) 69.916(2)
fl(deg) 89.349(2)
y(deq) 87.278(2)
V (A) 1793.7(4)
Z 2
Peld(gmabs coeff (mm )i 0.406
F(000) 736
crystal size (mm3) 0.15 x 0.08 x 0.02
0 range for data collection 1.08 to 27.500
limiting indices -11 no. of refns called 12358
no. of ind reflns (Rint) 8062 [R(int) = 0.0364]
completeness to 0= 22.500 97.8 %
absorption corr Integration
refinement method Full-matrix least-squares on F2
data / restraints / parameters 8062 / 0/405
GOFe on F2 0.964
R1,a avR2b [I > 20] 0.0477, 0.0957 [5629]
R1,a aR2b (all data) 0.0772, 0.1090
largest diff. peak and hole 0.723 and -0.490 e.A-3
R1 = C(||Fo| |Fc||)/ I|Fo|, wR2 = [C[w(Fo2 Fc2)2] / C[w(Fo2)2 1/2, S = [C[w(Fo2 Fc2)23
(n-p)]1/2, w= 1/[o2(Fo2)+(m*p)2+n*p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants.









Table 3-3. Crystal data and structure refinement for [tBuOCO]Mo(HNMe2)2C1(9
identification code (acl2)
empirical formula C42H53CIMON202
formula weight 749.25
T (K) 173(2)
At (A) 0.71073
crystal system Orthorhombic
space group Pbcn
a(A) 10.4875(8)
b (A+) 17.2088(13)
c (A) 21.1554(15)
a (deg) 90
fl (deg) 90


j(dee)
V (A )
Z


90
3 818.1(5)


Pcaled (Mg mm-3) 1.303
abs coeff (mm ) 0.450
F(000) 1576
crystal size (mm3) 0.15 x 0.08 x 0.08
8 range for data collection 1.93 to 27.490
limiting indices -13 no. of refns called 24328
no. of ind reflns (Rint) 4392 [R(int) = 0.0493]
completeness to 0= 22.500 99.9 %
absorption corr Integration
refinement method Full-matrix least-squares on F2
data / restraints / parameters 4392 / 0/223
GOFe on F2 1.241
R1,a avR2b [I > 20] 0.0263, 0.0771 [3320]
R1,a lR2b (all data) 0.0386, 0.0804
largest diff. peak and hole 0.331 and -0.380 e.A-3
R1 = C(||Fo| |Fc||)/ I|Fo|, wR2 = [C[w(Fo2 Fc2)2] / C[w(Fo2)2 1/2, S = [C[w(Fo2 F
(n-p)]1/2, w= 1/[o2(Fo2)+(m*p)2+n*p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants.


c2)2]










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BIOGRAPHICAL SKETCH

Adam Rand Carlson was bomn in 1979 in Cedar Rapids, Iowa. He graduated with a B.A. in

chemistry from The University of Northemn lowa in 2003. After graduation Adam spent two years

doing masters research in analytical chemistry at the University of Northemn Iowa. He came to the

University of Florida in 2005 and j oined the Veige Group. Upon completion of his M. S. program,

Adam moved to San Antonio, Texas and is currently employed with D.R. Horton.





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1 DESIGN AND SYNTHESIS OF EARLY TRANSITION METAL TRIANIONIC PINCER LIGANDS By ADAM RAND CARLSON A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIE NCE UNIVERSITY OF FLORIDA 2007

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2 2007 Adam Rand Carlson

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3 To my mom

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4 ACKNOWLEDG MENTS I thank Dr. Adam Veige and the entire Veige Group for their support. I would also like to thank Dr. K ha lil Abboud for my crystal structure data. I thank my parents for their loving encouragement, which motivated me to complete my study.

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5 TABLE OF CONTENTS p age ACKNOWLEDGEMENTS ................................ ................................ ................................ ............ 3 LIST OF TABLES ................................ ................................ ................................ .......................... 7 LIST OF F IGURES ................................ ................................ ................................ ........................ 8 LIST OF SCHEMES ................................ ................................ ................................ ..................... 10 LIST OF ABBREVIATIONS ................................ ................................ ................................ ....... 11 ABSTRACT ................................ ................................ ................................ ................................ .. 12 CHAPTER 1 INTRODUCTION ................................ ................................ ................................ ............ 13 C lassic Pincer Ligands ................................ ................................ ................................ ...... 13 Features of Pincer L igands ................................ ................................ ................................ 1 3 Examples of Pincer Ligands in C hemistry ................................ ................................ ........ 1 4 Previous Tria nionic Pincer R esults ................................ ................................ ................... 15 Modification of NCN Trianionic Pincer Ligands and New M etallation S chemes ........... 1 5 2 SYNTHESIS AND REACTIONS OF N C C C N PINCERS ................................ ............... 19 Synthesis and C haracterization of [2,4,6 MeArN C C C N]H 3 ( 3 ) and [3,5 CF 3 N C C C N]H 3 ( 4 ) ................................ ................................ ......................... 19 Synthesis and C haracterization of (2,6 i PrNCN)[Zr(NMe 2 ) 3 ] 2 ( 6 ) and [ (3 ,5 CF 3 N C C C N)Zr(NMe 2 ) 2 (NHMe 2 )] 2 ( 7 ) ................................ ................... 20 Synthesis and C haracterization of (3,5 CF 3 N C C C N)[Mo(NMe 2 ) 3 ] 2 ( 8 ) ....................... 21 Synthesis and C haracterization of [3,5 CF 3 N C C C N ]Mg(THF) 2 ( 10 ) ................................ 2 1 Synthesis and C haracterization of [3,5 CF 3 N C C C N]TMS 2 H ( 11 ) ................................ .... 22 Conclusions ................................ ................................ ................................ ....................... 24 Experimental ................................ ................................ ................................ ..................... 24 General Considerations ................................ ................................ ......................... 24 Synthesis of 2,2' (1,3 phenylene)diethanamine ( 2 ) ................................ .............. 25 Synthesis of N,N (2,2' (1,3 phenylene)bis(ethane 2,1 diyl)) bis(2,4,6 trimethylaniline) ( 3 ) ................................ ................................ ......... 25 Synthesis of N,N (2,2' (1,3 phenylene)bis(ethane 2,1 diyl)) bis(3,5 bis(trifluoromethyl)aniline) ( 4 ) ................................ ........................... 26 Synthesis of [ (3,5 CF 3 N C C C N)Zr(NMe 2 ) 3 HNMe 2 ] 2 ( 7 ) ................................ ... 27 Synth esis of (3,5 CF 3 N C C C N)[Mo(NMe 2 ) 3 ] 2 ( 8 ) ................................ ............. 27 Synthesis of [ (3,5 CF 3 N C C C N]HMg(THF) 2 ( 10 ) ................................ ............. 28 Synthesis of [3,5 CF 3 N C C C N]H(SiMe 3 ) 2 ( 11 ) ................................ ..................... 28

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6 page X ray Experimental Det ails F o r [3,5 CF 3 N C C C N]H 3 ( 4 ) ................................ .... 29 X ray Experimental Details F or (2,6 i PrNCN)[Zr(NMe 2 ) 3 ] 2 ( 6 ) ..................... 30 X ray Experimental Details F or [ (3,5 CF 3 N C C C N)Zr(NMe 2 ) 3 HNMe 2 ] 2 ( 7 ) .... 30 X ray Experimental Details F or [ (3,5 CF 3 N C C C N]HMg(THF) 2 ( 10 ) .............. 31 3 SYNTHESIS AND REACTIVITY OF TERPHENYL OCO 3 PINCER COMPLEXES ................................ ................................ ................. 55 Synthesis and C haracterization of terphenyl [ t BuOCO]H 3 ( 17 ) ................................ ....... 55 Synthesis and C haracterization of [ t BuOCO]MoNMe 2 (HNMe 2 ) 2 ( 18 ) ............................ 5 6 Synthesis and C haracterization of [ t B uOCO]MoCl ( 19 ) ................................ ................. 5 7 Conclusions ................................ ................................ ................................ ....................... 58 Experimental ................................ ................................ ................................ ..................... 58 General Considerations ................................ ................................ ......................... 58 Synthesis of 2 bromo 6 tert butylphenol ( 13 ) ................................ ...................... 59 Synthesis of 1 bromo 3 tert butyl 2 methoxybenzene ( 14 ) ................................ 59 Synthesis of 1,3 dibromo 2 iodobenzene ( 15 ) ................................ ..................... 60 di tert butyl dimethoxy 1,1 terphenyl ( 16 ) ........... 60 di tert butyl terphenyl diol ([ t BuOCO]H 3 ) ( 17 ) ................................ ........................ 60 Synthesis of [ t BuOCO]MoNMe 2 (HNMe 2 ) 2 ( 18 ) ................................ .................. 61 Synt hesis of [ t BuOCO]Mo(HNMe 2 ) 2 Cl ( 19 ) ................................ ........................ 62 X ray Experimental Details F or [ t BuOCO]MoNMe 2 (HNMe 2 ) 2 ( 18 ) .................. 62 X ray Experimental Details F or [ t BuOCO]Mo(HNMe 2 ) 2 Cl ( 19 ) ........................ 63 LIST OF REFERENCES ................................ ................................ ................................ .............. 76 BIOGRAPHICAL SKETCH ................................ ................................ ................................ ........ 79

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7 LIST OF TABLES Table page 2 1 Selected angles and bond lengths for crystal structures 6 7 and 10 ................................ 59 2 2 Crystal data, structure solution and refinement for [3,5 CF 3 N C C C N]H 3 ( 4 ) .................... 51 2 3 Crystal data and structure refinement for (2,6 i PrNCN)[Zr(NMe 2 ) 3 ] 2 ( 6 ) ................... 52 2 4 Crystal data and structure refinement for [ ( 3,5 CF 3 N C C C N)Zr(NMe 2 ) 3 HNMe 2 ] 2 ( 7 ) ................................ .............................. 53 2 5 Crystal data and structure refinement for [ (3,5 CF 3 N C C C N]HMg(THF) 2 ( 10 ) ........... 54 3 1 Selected angles and bond lengths for crystal structures 18 and 19 ................................ ... 73 3 2 Crystal data and structure refinement for [ t BuOCO]MoNMe 2 (HNMe 2 ) 2 ( 18 ) ................. 74 3 3 Crystal data and structure refinement for [ t BuOCO]Mo(HNMe 2 ) 2 Cl ( 19 ) ....................... 75

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8 LIST OF FIGURES Figure page 1 1 Format of classic pincer ligands ................................ ................................ ....................... 17 1 2 Pincer catalyzed reactions ................................ ................................ ................................ 17 1 3 Hard Hard ................................ ................................ .. 17 1 4 PO V ray diagram of 2,6 i PrArNCN Zr and 2,6 i PrArNCN Ti ................................ ..... 18 2 1 ORTEP diagram of [3,5 CF 3 N C C C N]H 3 ( 4 ) ................................ ................................ ..... 34 2 2 ORTEP diagram of (2,6 i Pr NCN)[Zr(NMe 2 ) 3 ] 2 ( 6 ) ................................ ........................ 35 2 3 ORTEP diagram of (3,5 CF 3 N C C C N)[Zr(NMe 2 ) 2 (HNMe 2 )] 2 ( 7 ) ................................ 36 2 4 ORTEP diagram of [ (3,5 CF 3 N C C C N]HMg(THF) 2 ( 10 ) ................................ .............. 37 2 5 1 H NMR spectra of 2,2' (1,3 phenylene)diethanamine ( 2 ) in C 6 D 6 ................................ 38 2 6 1 H NM R spectra of [2,4,6 MeN C C C N]H 3 ( 3 ) in C 6 D 6 ................................ ...................... 39 2 7 1 H NMR spectra of [3,5 CF 3 N C C C N]H 3 ( 4 ) in C 6 D 6 ................................ ........................ 40 2 8 13 C{ 1 H} NMR spectrum of [3,5 CF 3 N C C C N]H 3 ( 4 ) in C 6 D 6 ................................ ........... 41 2 9 1 H NMR spectr a of [ (3,5 CF 3 N C C C N)Zr(NMe 2 ) 3 HNMe 2 ] 2 ( 7 ) in C 6 D 6 ..................... 42 2 10 13 C{ 1 H} NMR spectrum of [ (3,5 CF 3 N C C C N)Zr(NMe 2 ) 3 HNMe 2 ] 2 ( 7 ) in THF d 8 ...... 43 2 11 1 H NMR spectra of (3,5 CF 3 N C C C N)[Mo(NMe 2 ) 3 ] 2 ( 8 ) in C 6 D 6 ................................ 44 2 12 13 C{ 1 H} NMR spectrum of (3,5 CF 3 N C C C N)[Mo(NMe 2 ) 3 ] 2 ( 8 ) in C 6 D 6 .................... 45 2 13 1 H NMR spectra of [3,5 CF 3 N C C C N]HMg(THF) 2 ( 10 ) in Tol d 8 @ 75 C .................... 46 2 14 1 H NMR spectra of [3,5 CF 3 N C C C N]H(SiMe 3 ) 2 ( 11 ) in C 6 D 6 ................................ ......... 47 2 15 13 C{ 1 H} NMR spectrum of [3,5 CF 3 N C C C N]H(SiMe 3 ) 2 ( 11 ) in C 6 D 6 ............................. 48 2 16 19 F NMR spectrum of [3,5 CF 3 N C C C N]H(SiMe 3 ) 2 ( 11 ) in C 6 D 6 ................................ ..... 49 3 1 ORTEP diagram of [ t BuOCO ] MoNMe 2 (HNMe 2 ) 2 ( 18 ) ................................ ................... 65

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9 Figure page 3 2 ORTEP diagram of [ t BuOCO ] Mo(HNMe 2 ) 2 Cl ( 19 ) ................................ ........................ 66 3 3 1 H NMR spectrum of [ t BuOCO]H 3 ( 17 ) in acetone d 6 ................................ ..................... 67 3 4 13 C NMR spectrum of [ t BuOCO]H 3 ( 17 ) in C 6 D 6 ................................ ............................. 68 3 5 1 H NMR spectrum of [ t BuOCO] MoNMe 2 (HNMe 2 ) 2 ( 18 ) in THF d 8 ............................. 69 3 6 13 C NMR spectrum of [ t BuOCO] MoNMe 2 (HNMe 2 ) 2 ( 18 ) in THF d 8 ............................. 70 3 7 1 H NMR spectrum of [ t BuOCO] Mo(HNMe 2 ) 2 Cl ( 19 ) in C 6 D 6 ................................ ....... 71 3 8 13 C NMR spectrum of [ t BuOCO] Mo(HNMe 2 ) 2 Cl ( 19 ) in THF d 8 ................................ .. 72

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10 LIST OF SCHEMES Scheme page 1 1 Formation of group 4 NCN metal complexes ................................ ................................ ... 16 1 2 Metallation via trimethylsilyl halide elimination ................................ ............................. 16 1 3 Metallation via amine extrusion ................................ ................................ ........................ 16 2 1 Synthesis of ArN C C C NH 3 (where Ar = 2,4,6 MeC 6 H 3 ( 3 ) and 3,5 CF 3 C 6 H 3 ( 4 )) ........... 32 2 2 Synthesis of 6 and 7 (where Ar = 2,4 i PrC 6 H 3 ( 6 ) and 3,5 CF 3 C 6 H 3 ( 7 ) ......................... 32 2 3 Synthesis of the molybdenum dinuclear species (3,5 CF 3 N C C C N)[Mo(NMe 2 ) 3 ] 2 ( 8 ) ................................ ................................ ........ 33 2 4 Synthesis of the dimagnesio salt [3,5 CF 3 N C C C N]H[MgCl(THF) 2 ] 2 ( 9 ) and the minor impurity monomagnesio salt [ (3,5 CF 3 N C C C N]HMg(THF) 2 ( 10 ) .............. 33 2 5 Synthesis of the bistrimethylsilyl species [3,5 CF 3 N C C C N]H (SiMe 3 ) 2 ( 11 ) .................... 33 3 1 Synthesis of [ t BuOCO]H 3 ( 17 ) ................................ ................................ ......................... 64 3 2 Synthesis of [ t BuOCO ] MoNMe 2 (HNMe 2 ) 2 ( 18 ) ................................ .............................. 64 3 3 Synthesis of [ t BuOCO] Mo(HNMe 2 ) 2 Cl ( 19 ) ................................ ................................ .... 65

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11 LIST OF ABBREVIATIONS ECE electron donor carbon electron donor pincer ligands e electron M C a metal carbon bond i Pr iso propyl t Bu tert butyl EDG electron donating group EWG electron widthdrawing group PCP phosphorous carbon phosphorous NCN nitrogen carbon nitrogen pi ncer ligands OCO oxygen carbon oxygen pincer ligand NMR nuclear magnetic resonance HRMS high resolution mass spectrometry

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12 Abstract of Thesis Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements fo r the Degree of Master of Science DESIGN AND SYNTHESIS OF EARLY TRANSITION METAL TRIANIONIC PINCER LIGANDS B y Adam Rand Carlson December 2007 Chairman: Adam Veige Major : Chemistry The chemistry of trianionic pi ncer ligands is largely unknown, but prelimina ry synthetic studies establish their terdentate coordination behavior. Early transition metals differ greatly in reactivity and coordination compared with late transition metals. Classic pincer ligands have on metals and are not well suited for early transition metals. New trianionic pincer ligand s utilize hard Appropriate conditions for coordination of trianionic pincer ligands to e arly transition metals must be developed. Pincer ligands are easily modified and are not limited to a single method of metallation. This thesis describes the synthesis and reactivity of new trianionic pincer ligands NCN 3 and OCO 3 with grou p 4 and 6 early transition metals

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13 CHAPTER 1 INTRODUCTION Classic Pincer Ligands The first mention of a pincer ligand in the literature was by Shaw in 1976. He described a PCP pincer review coordinated to rhodium(III), iridium(III), palladium(II) and platinum(II) (group 9 and 10) metal ions. 1 5 Pincer ligated metal complexes, when used in homogeneous metal catalysis, can promote efficient chemical transformations. Today these complexes are used with great success in a wide range of industrial and fin e chemical syntheses. 6 13 Features of Pincer L igands Pincer ligands share two salient features, the most important being the presence of a central metal bond. This metal carbon (M C) bond renders complexes thermally robust and prevents dissociation from the metal even at high temperatures, leading to high turnover numbers. This M C bond carries a single negative charge, making the majority of pincer ligands monoanionic. The second characteristic of classic pincer ligands is the presence of two ne utral, two electron donor atoms attached via methylene spacers at the 2 and 6 positions of the aryl backbone. Tertiary phosphines such as those first used by Shaw were initially used as donor atoms, but the incorporation of other neutral 2e donors ( Figu re 1 1) into the structure has led to the complexation of a wide range of transition metals. 1 4 These two electron donors are typically altered to enable control of electron density at the metal. The terdentate binding of a pincer ligand to metals increases the stability of the organometallic complex relative to mono or bidentate ligands. The terdentate motif also serves to enable greater control over accessibility to the metal, and therefore substrate binding, since the ligand occupies three coordination sites.

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14 Further tailoring of this modular architecture by the addition of electron withdrawing (EWG) or electron donating (EDG) groups to the aryl backbone can fi ne tune the electron density at the metal. 1 5 Examples of Pincer Ligands in C hemistry The variety of chemical transformations that can be catalyzed by pincer ligand systems is beyond the scope of this thesis 1 6 but a few examples are shown below ( Figure 1 2 ) 1 7 1 8 These reactions include poly olefin 19 alkane and cycloalkane dehydrogenation, Suzuki coupling s, 2 0 Heck reactions aldol reactions, cyclopropanations, allylation of alcohols, allylic alkylation, hydrogenation of ketones, Kharasch additions 2 1 and M ichael reactions To date the majority of useful pincer related catalysts have used the expensive late metals. The main objective for this project is to tailor a pincer ligand so that it will accommodate the specific demands of cheaper early transition m etals. The problem with using a classic pincer ligand design to form an early transition metal complex, is that early and late transition metals differ significantly in their properties. Generally, late transition metals favor low oxidation states, are l ow coordinate and are tolerant of many functional groups. 2 2 2 5 By contrast, early transition metals favor high oxidation states and are intolerant of many functional groups. In a classic pincer ligand, the interaction between the pendant arms and the met al is a lone hard metal center. This is ideal for late transition metals, The hard nature of the early transition metals necessitates modification of the pincer ft hard hard

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15 binding motif ( Figure 1 3 ). This hard donation can be accomplished via a localized electron pair N or O Because early transition metals are electro p ositive this hard interaction stabilizes higher oxidation states. A trianionic pincer ligand serves to occupy three coordination sites of the metal and at least stabilize oxidation state of 3 + As with late transition metal pincer systems a halide tran s to the M C bond serves to promote functionalization of the complex, or allow for entry into various catalytic cycles. This halide contributes to produce a 4 + oxidation state with a trianionic pincer ligand. The 4 + oxidation state is common for our targ et group 4 and 6 metals. Previous T rianionic Pincer R esults The first generation trianionic pincer ligands successfully ligated all of the group 4 metals (Ti, Zr, Hf) by using a trilithio salts of the parent NCN ligand ( Scheme 1 1). However, when applied to group 6 metals only intractable mixtures were produced. This was presumably due to electron transfer reduction of the metal substrate Early transition metals are especially susceptible to these side reactions during R Li salt metathesis. X ray cryst al structures of the group 4 metal NCN complexes did reveal very small N M N bond angles of ~140 ( Figure 1 4) compared with N M N bond angles of ~160 for late transition metals. 26 2 7 Based on these results we sought to make a change to the NCN pincer de sign, and explore alternative routes to metallation. Modification of NCN T rianionic P incer L igands and N ew M etallation S chemes The first change needed was an increase in the length of the pendant arms from single methylene spacers. Inserting an additional methylene spacer to form N C C C N derivatives would produce two six membered rings once chelated, but more importantly would allow for changes in metal atomic radii during reaction sequences. The second change was a modification of our

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16 approach to metallati on. One of the benefits of using hard donor atoms is the ease of functionalization thus enabling different metallation schemes. The donor atoms can be modified to include functional groups such as SiMe 3 which have been shown to eliminate trimethylsilylh alides when reacted with metal halides. 2 8 This method serves to chelate the metal followed by stepwise alkylation of the metal that can form the final M C bond ( Scheme 1 2 ). While lithium salts were used successfully to ligate group 4 metals sodium and potassium salts are an alternative for group 6 metals. In addition, protonated ligands can be reacted directly with metal dialkylamides which eliminates dialkylamine ( Scheme 1 3 ). Scheme 1 1. Formation of group 4 NCN m etal complexes. Scheme 1 2. Metallation via trimethylsilyl halide elimination. Scheme 1 3. Metallation via amine extrusion.

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17 Figure 1 1. Format of c lassic pincer ligands. Figure 1 2. Pinc er catalyzed reactions. Figure 1 3 Hard Hard motifs.

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18 Figure 1 4. POV ray di agram of 2,6 i PrArNCN Zr and 2,6 i PrArNCN Ti Selected bond angles; N2 Zr N1 = 140.11, N1 Ti N2 = 144.46

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19 CHAPTER 2 SYNTHESIS AND METALLATION OF N C C C N PINCER LIGANDS Synthesis and C haracterization of [2,4,6 Me ArN C C C N]H 3 (3 ) and [3,5 CF 3 N C C C N]H 3 (4) Th e most direct synthesis of our target N C C C N pincer ligands utilizes diamine 2 This starting material allows for easy access to a variety of pincer ligands via cross coupling with any commercially available bromobenzene. Diamine 2 is not commercially ava ilable, but can be synthesized by reduction of dicyano 1 with LiAlH 4 29 Diamine 2 was obtained in 33% yield following purification by distillation. The identity of 2 was verified by 1 H NMR spectroscopy. The two sets of methylene protons are observed as triplets that integrate to four protons each and appear at 2.88 and 2.65 ppm. A corresponding broad singlet is observed at 1.01 ppm and is ascribed to the two NH protons. Diamine 2 was then used in a Buchwald Hartwig cross coupling reaction 30 ,3 1 with 1 bromomesitylene or 3,5 trifluoromethylbromobenzene to produce ligand 3 and 4 in 61% and 33% yield respectively ( Scheme 2 1 ). A 1 H NMR spectrum of 3 revealed the expected two sets of methylene protons as a doublet of triplets at 3.08 ppm and a triplet at 2.80 ppm. The key feature of the spectrum for 3 are two singlets corresponding to the methyl groups in the 2, 4, and 6 positions which and appear at 2.15 and 2.06 ppm in a 6:12 ratio respectively. The 1 H NMR spectrum of 4 is similar, as expected to 3 A doublet of triplets and triplet at 3.73 and 2.38 ppm are observed for the two sets of methylene protons. The most indicative peak of the molecule is a singlet at 6.48 ppm corresponding to the four protons in the 2 and 6 positions of the trifluoromethy l aryl rings. The unique position of this peak is used to monitor the progression of metallation reactions. Although ligand 3 is as an oil, 4 is easily crystallized from saturated pentane solutions. The increased crystallinity of 4 can be attributed to the trifluoromethyl groups. The molecular structure, determined by X ray crystallography is

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20 presented in Figure 2 1 and shows a staggered stacking arrangement of three trifluoromethyl rings from two independent ligand molecules. A table of pertinent bond lengths and angles is presented in Table 2 1. The combined spectroscopic analysis and X ray experiment confirmed the identity of 4 Synthesis and C haracterization of (2,6 i PrNCN)[Zr(NMe 2 ) 3 ] 2 (6) and [ (3,5 CF 3 N C C C N)Zr(NMe 2 ) 2 (NHMe 2 )] 2 (7) Previous work in the Veige group was centered on the NCN derivative 5 in which only one methylene group is present in the pincer arm. When 5 is tr eated with Zr(N Me 2 ) 4 the bimetallic complex 6 is formed ( Scheme 2 2 ) which was characterizaed by X Ray crystallographyand the structure is presented in Figure 2 2 The zirconium remains in a tetrahedral geometry with three coordination sites occupied by dimethylamide ligands. In contrast ligation of Zr(NMe 2 ) 4 with 4 produced dimer 7 in which each ligand occupies an axial and equatorial site of opposing metal centers. The molecular structure is presented in Figure 2 3 One coordinated dimethylamide grou p remains and is located trans to the ligand amide bond. The coordinated dimethylamine is distinguished from the amides by its tetrahedral geometry and the remaining amides are planar. The zirconium center has a distorted trigonal bipyramidal geometry, w ith the equatorial amides separated by 114.44(11) to 122.10(10) and the axial nitrogen atoms lying 174.00(10) apart ( Table 2 1 ). Although ligand 4 did not chelate the metal as hoped, some information was obtained from the difference in reactivity betwee n 4 and 5 Clearly by moving the alkyl groups to the 3,5 positions allowed for the formation of a symmetric dimer that contained two bridging ligands whereas the sterically bulky i Pr groups only allowed one ligand to bridge. The influence of alkyl group size in reactions with Zr(NMe 2 ) 4 was also probed by Lappert and coworkers. 32 A

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21 compound analogous to 6, with 2,6 methyl groups was reported to dimerize and incorporate two bridging ligands under similar reaction conditions. Synthesis and C haracterization of (3,5 CF 3 N C C C N)[Mo(NMe 2 ) 3 ] 2 (8) Additional reactivity differences between 4 and 5 are observed when treated with Mo(NMe 2 ) 4 Ligand 5 proved unreactive, even when heated to reflux in toluene for 18 hours. The lack of reactivity with Mo(NMe 2 ) 4 is due to proximity and size of the 2,6 i Pr groups. By comparison, treatment of 4 with Mo(NMe 2 ) 4 resulted in coordination of the amide groups to Mo. While less than 2.5 equiv of Mo(NMe 2 ) 4 did not consume all of 4 a bimetallic product could by detected by 1 H N MR spectroscopy when 3 equivalents were employed ( Scheme 2 3 ) After heating the reagents at 40 C for 4 d a product was isolated by removal of all volatiles in vacuo and then subliming the remaining Mo(NMe 2 ) 4 The product is tentatively assigned as the bimetallic complex (3,5 CF 3 NCN)[Mo(NMe 2 ) 3 ] 2 ( 8) and is characterized by 1 H NMR spectroscopy. The two sets of methylene protons appear as triplets at 3.73 and 2.84 ppm. A large singlet at 3.08 ppm that integrates to 36 protons is assigned to the methyl protons of 6 equivalent dimethylamide ligands. This supports the assignment of two molybdenum atoms that coordinate 3 equivalent dimethylamides each, as in the crystallographically determined structure of 6 above. Synthesis and C haracterization of [3,5 CF 3 N C C C N]Mg(THF) 2 ( 10 ) To avoid the slow reactivity with metal dialkylamides we investigated a trimethylsilylhalide (TMSX) elimination route. By attaching TMS groups to the nitrogen atoms of 4 we hoped to eliminate TMSX from metal halide precursors which are commercially available and offer abundant variations with respect to choice of transition metal and oxidation state. The first step in creating TMS derivatives of 4 requires the synthesis of a dimagnesio salt,

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22 which led to an interesting observation. When 4 is treated with MeMgCl and after removal of THF the chelated magnesium product [3,5 CF 3 N c C c N]Mg(THF) 2 ( 10 ) was extracted with pentane and single crystals were obtained ( Scheme 2 4 ). This N,N chelated product is a side product and is only obtained in a minimal yield, however, enough was isolated to enable both low temperature 1 H NMR spectroscopy and X ray structure determination. The X ray structure ( Figure 2 4 ) obtained at 173 K indicates that the magnesium is oriented such that the ipso aryl C H bond is positioned directly over the metal center. The tetrahedral coordination sphere is comprised of the two amides from the ligand and two oxygen atoms from coordinated THF molecules. After chelation of the amides it is apparent that the ligand is in the correct conformation for C H activation by a metal. This result provides insight into a potential metallation route in which the arms first attach and then the backbone C H bond is activated. While this confirms pendant arm chelation as a possible route to installing trianionic ligands on target metals the magnesium in this complex is unable to accomplish this as it is lacks an accessible higher oxidation state. In the 1 H NMR spectrum the protons in the coordinated THF molecules are shifted 0.5 p pm upfield. The methylene and coordinated THF protons are fluxional on the NMR time scale resulting in their appearance as broad peaks at ambient temperature. As the temperature is reduced to 75 C the protons in the ligand methylene groups begin to res olve away from the THF protons. Unfortunately the low yield of 10 prevented further investigation and the synthesis of the [3,5 CF 3 N c C c N]TMS 2 H ( 11 ) was conducted by in situ preparation of a dimagnesio salt. Synthesis and C haracterization of [3,5 CF 3 N C C C N]TMS 2 H ( 11 ) The N,N TMS derivative 11 was formed by treating 4 with 2.1 equiv of methyl Grignard, followed by addition of 3 equiv of TMSCl. 1 1 is obtained as a white crystalline solid in 74%

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23 yield ( Scheme 2 5 ). The 1 H NMR spectrum of 11 revealed the ex pected signals for the methylene groups and the singlet from the ortho aryl protons formerly at 6.48 ppm for ligand 4 shifted to 7.35 ppm. The prominent feature of the spectra is the singlet at 0.00 ppm which is assigned to the six methyl groups from two trimethylsilyls. Integration of the singlet from the TMS groups only indicates fifteen protons, rather than the expected eighteen. This can be attributed to a difference in relaxation times for these protons though they were not determined and the identi ty of 11 was confirmed by additional means. 19 F NMR shows only one sharp singlet at 63.32, indicating only one compound is formed and a 13 C NMR spectrum indicated the presence of twelve peaks, the largest attributed to the SiMe 3 carbons at 0.75 ppm. Li gand 1 1 was treated with TiCl 4 ZrF 4 TaF 5 ZrI 4 and MoCl 5 in refluxing toluene or xylenes for 12 24 hr periods. The 1 H NMR spectrum of the ZrF 4 reaction mixture showed only 1 1 even after 20 hrs in refluxing xylenes, indicative of the thermal stability o f the ligand. Reactions with TaF 5 ZrI 4 and MoCl 5 gave products whose NMR spectra were consistent with the parent ligand 4 This occurred even after care was taken to silylate all glass surfaces to reduce the likelihood that protons were coming from the glassware. The presence of TMSI and TMSCl in the 1 H NMR spectra indicated that the ligand was reacting with metal halides, but was not anchoring via C H bond activation of the backbone. Only reactions with TiCl 4 showed the presence of a product (in the 1 H NMR spectra up to 33%). The 1 H NMR spectra showed new peaks attributed to the two pairs of methylene protons at 3.72 and 2.55 ppm. The position of these suggests a new product was formed with titanium. The product was never isolated and pale yellow crystals were grown but deteriorated before X ray analysis could be conducted.

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24 Conclusion s Metallation attempts with ligand 4 revealed two problems. Lack of rigidity promotes dimerization and sterics force the two pendant arms apart. This is further c omplicated by slow reactivity in aminolysis reactions. Without a driving force to chelate a single metal or without the pendant arms being forced together, ligand 4 has an affinity for dimerization. The TMS halide elimination metallation route has simila r drawbacks. While metal chelated pincers are very robust, the high temperatures used to promote reactions of 11 with metal halides ultimately lead to N M bond protonation. While this remains a viable route to metallation, it will require additional modi fication of the NCN ligand. Experimental General Considerations Unless specified otherwise, all manipulations were performed under an inert atmosphere using standard Schlenk or glovebox techniques. Pentane, hexanes, toluene, diethyl ether, tetrahydrofu ran, and 1,2 dimethoxyethane were dried using a GlassContour drying column. C 6 D 6 and toluene d 8 (Cambridge Isotopes) were dried over sodium benzophenone ketyl, distilled or vacuum transferred and stored over 4 molecular sieves. THF d 8 (Cambridge Isotop es) was stored over 4 sieves and used without further purification. Sublimed Zr(NMe 2 ) 4 was purchased from Strem Chemicals and used without further purification. LiAlH 4 (95%), m xylylenedicyanide (99%), and 2 bromomesitylene (99%), were purchased from A cros and used as received. Pd 2 (dba) 3 3,5 bis(trifluoromethyl)bromobenzene, MeMgCl (3.0 M in THF), and chlorotrimethylsilane (97%) were purchased from Aldrich and used as received. rac BINAP was purchased from Fluka and used as received. Mo(NMe 2 ) 4 was synthesized according to the procedure from Chisholm et al 3 3

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25 NMR spectra were obtained on Gemini (300 MHz), VXR (300 MHz), or Mercury (300 1 H and 13 C NMR spectra, the residual protio or ca rbon solvent peak were referenced as an internal reference. GC/MS spectra were recorded on an Agilent 6210 TOF MS instrument. C, H, and N elemental analysis were determined by Robertson Microlit Laboratories Inc. and Complete Analysis Laboratories. Synth esis of 2 ,2' (1,3 phenylene)diethanamine (2 ) An alternative synthesis of 2 was performed. 3 4 Under argon flow diethyl ether (500 mL) was added to LiAlH 4 (60 g, 12.7 equiv, 1.58 mmol) in a 1000 mL three neck flask fitted with a reflux condenser, a 500 mL d ropping funnel and a stirbar. To the dropping funnel was added m xylylene dicyanide ( 1 ) (19.4 g, 0.124 mol) in diethyl ether (300 mL). The m xylylene dicyanide solution was added dropwise under static argon over a period of 2 h with vigorous stirring and then refluxed for 48 h. The resulting green suspension was cooled to 0 C and then water (100 mL) was added dropwise through the dropping funnel, followed by a 15% by wt. solution of NaOH (100 mL). Extra diethyl ether was added periodically. An additio nal 30 mL of water was added to produce a free flowing white suspension. Compound 2 was extracted from the white suspension with diethyl ether (6 x 150 mL) and each portion was dried over Na 2 SO 4 then condensed in vacuo and combined. The transparent yello w oil was purified by distillation at 170 C @ 20 mTorr. Yield 6.0 g (0.036 mol, 39.0%). 1 H NMR (300 MHz, C 6 D 6 7.15 (t, J = 7.30 Hz, 1H, Ar H), 6.99 (s, 1H, Ar H), 6.97 (s, 2H, Ar H), 2.88 (t, J = 6.86 Hz, 4H, NH 2 C H 2 ), 2.65 (t, J = 6.86 Hz, 4H, C H 2 Ar), 1.01 (br. s, 4H, N H 2 ). Synthesis of N,N (2,2' (1,3 phenylene)bis(ethane 2,1 diyl))bis(2,4,6 trimethylan iline) (3 ) To a 100 mL round bottom flask charged with a stir bar and toluene (50 mL) were added 2 (0.920 g, 5.61 mmol), 2 bromomesitylene (2.230 g, 2 equiv, 11.22 mmol), Pd 2 (dba) 3 (0.080 g,

PAGE 26

26 0.5%, 0.087 mmol), rac BINAP (0.140 g, 1.5%, 0.219 mmol), and NaO t Bu (1.617 g, 16.83 mmol). After refluxing for 72 h under argon the solution was filtered through celite while hot and the remaining toluene was removed in vacuo Nonvolatile products were then taken up in hot pentanes and filtered again through celite. The final product was produced as a light red oil after volatiles were removed in vacuo Yield 1.36 g (3.4 mmol, 61%). 1 H NMR (300 MHz, C 6 D 6 7.14 (s, 1H, ipso Ar H), 7.08 (t, J = 7.61 Hz, 1H, Ar H), 6.91 (d, J = 5.97 Hz, 2H, Ar H), 6.75 (s, 4H, Ar H), 3.08 (dt, J = 6.86 Hz, J = 0.86 Hz, 4H, N C H 2 ), 2.80 (t, J = 7.01 Hz, 2H, NH), 2.63 (t, J = 6.86 Hz, 4H, Ar C H 2 ), 2.15 (s, 6H, Ar 4 C H 3 ), 2.06 (s, 12H, Ar 2,6 C H 3 ). Synthesis of N,N (2,2' (1,3 phenylene)bis(ethane 2,1 diyl))bis(3 ,5 bis(trifluoromet hyl)aniline) (4 ) To a 100 mL round bottom flask charged with a stir bar and toluene (50 mL) were added 2 (1.500 g, 9.15 mmol), 3,5 bis(trifluoromethyl) bromobenzene (5.370 g, 2 equiv, 18.3 mmol), Pd 2 (dba) 3 (0.130 g, 0.5%, 0.142 mmol), rac BINAP (0.228 g, 1. 5%, 0.357 mmol), and NaO t Bu (2.637 g, 27.5 mmol). After refluxing for 72 h under argon the solution was filtered through celite while hot and the remaining toluene was removed in vacuo Nonvolatile products were then taken up in hot pentanes and filtered through celite again. The final product was recrystallized two times in pentane at 20 C. Yield 2.1 g (3.57 mmol, 39.0%). 1 H NMR (300 MHz, C 6 D 6 7.22 (s, 2H, Ar H), 7.11 (t, J = 7.64 Hz, 1H, Ar H), 6.81 (dd, J = 7.64, 1.70 Hz, 2H, Ar H), 6.72 (s, 1H, Ar H), 6.48 (s, 4H, Ar H), 3.13 (t, J = 5.52 Hz, 2H, NH), 2.73 (dt, J = 6.94 Hz, 4H, NH C H 2 ), 2.38 (t, J = 6.94 Hz, 4H, C H 2 Ar). 13 C{ 1 H} NMR ( 128.39 Hz, C 6 D 6 35.35 (s, C H 2 Ar), 44.62 (s, HN C H 2 ), 110.38 (s, aromatic), 112.27 (s, aromatic), 122.85 (s, aromatic), 126.47 (s, aromatic), 127.60 (s, aromatic), 129.71 (s, aromatic), 132.97 (q, J = 32.74 Hz, C F 3 ), 139.76 (s, Ar C CH 2 ), 149.16 (s, Ar C NH ). HRMS calculated (found) for C 26 H 20 F 12 N 2 (M+H + ) 589.1508 (589.1537).

PAGE 27

27 Synthesis of [ (3,5 CF 3 N C C C N ) Zr(NMe 2 ) 3 HNMe 2 ] 2 (7) A solution of Zr(NMe 2 ) 4 (45 mg, 0.170 mmol) in toluene (1 mL) was added to 4 (100 mg, 0.170 mmol) in toluene (1 mL) at 3 5 C with stirring. After warming to ambient temperature and stirring for 3 h, volatiles from the resulting brown solution were removed in vacuo The product was recrystallized from concentrated solutions of 7 in toluene over a period of 7 days. 1 H NMR (300 MHz, THF D 8 7.39 6.98 (m, 18H (11H), Ar H), 3.78 (t, J = 8.49 Hz, 4H, N C H 2 ), 3.13 (s, 12H, N(C H 3 ) 2 ), 2.77 (t, J = 7.64 Hz, 4H, Ar C H 2 ), 2.31 (s, 6H, HN(C H 3 ) 2 ), 2.28 (s, 1H, H N(CH 3 ) 2 ). 13 C{ 1 H} NMR ( 67.57 Hz, THF D 8 21.52 (s, HN( C H 3 ) 2 ), 3 5.24 (s, N C H 2 ), 36.07 (s, N C H 2 ), 39.36 (s, N( C H 3 ) 2 ), 43.04 (s, N( C H 3 ) 2 ), 45.57 (s, Ar C H 2 ), 50.02 (s, Ar C H 2 ), 109.57 (s, aromatic), 112.22 (s, aromatic), 115.75 (s, aromatic), 123.38 (s, aromatic), 126.08 (s, aromatic), 127.33 (s, aromatic), 128.9 5 (s, aromatic), 129.72 (s, aromatic), 133.30 (q, J = 32.0 Hz, C F 3 ), 141.02 (s, aromatic), 155.53 (s, aromatic). Anal. Calcd for C 64 H 74 F 24 N 10 Zr 2 (2 C 6 D 6 ) C, 50.95; H, 4.13; N, 7.82. Found: C, 49.28; H, 4.50; N, 5.83. Synthesis of (3,5 CF 3 N C C C N)[Mo(NMe 2 ) 3 ] 2 (8) To a 50 mL sealed ampule charged with a stir bar and toluene (25 mL) were added [3,5 CF 3 N c C c N]H 3 (4) (250 mg, 0.425 mmol), and Mo(NMe 2 ) 4 (350 mg, 1.275 mmol). After heating to 40 C for 4 d all volatiles were removed in vacuo The remaining purp le solid was gently heated in vacuo to 50 C for 48 h to sublime the unreacted Mo(NMe 2 ) 4 1 H NMR (300 MHz, C 6 D 6 7.34 (br. s, 1H, ipso Ar H), 7.14 (br. s, 2H, Ar H), 7.11 (br. s, 2H, Ar H), 7.05 (br. s, 2H, Ar H), 7.03 (br. s, 1H, Ar H), 7.01 (br. s, 1H, Ar H), 3.73 (t, J = 8.35 Hz, 4H, N C H 2 ), 3.08 (br. s, 36H, N(C H 3 ) 2 ), 2.84 (t, J = 7.76 Hz, 4H, Ar C H 2 ). 13 C{ 1 H} NMR ( 67.57 Hz, C 6 D 6 128.39 37.58 (s, C H 2 Ar), 50.50 (s, N( C H 3 ) 3 ), 56.52 (s, N C H 2 ), 110.91 (s, aromatic),

PAGE 28

28 116.48 (s, aromatic), 126.91 (s, aromatic), 127.33 (s, aromatic), 129.59 (s, aromatic), 129.76 (s, aromatic), 132.88 (q, J = 32.06 Hz, C F 3 ), 140.82 (s, aromatic), 156.39 (s, aromatic). Synthesis of [ (3,5 CF 3 N C C C N]HMg(THF) 2 (10) MeMgCl (1.30 mL, 3.0 M, 3.9 mmol) in THF (2 mL) was added dropwise to [3,5 CF 3 N c C c N]H 3 ( 4 ) (1.0g, 1.70 mmol) in THF (2 mL) with a magnetic stirbar at 35 C. Aft er 3 h volatiles were removed in vacuo and a dark yellow powder remained. Pentanes (3 mL) were added to the powder and stirred for 12 h. The suspension was filtered and white needle crystals were grown from a concentrated solution of the filtrate at 35 C over a period of 48 h. Enough product was produced for x ray analysis and 1 H NMR but not for EA or 13 C{ 1 H} NMR spectroscopy. 1 H NMR (300 MHz, Tol D 8 75 C 7.25 (s, 2H, Ar H), 7.16 (s, 2H, Ar H), 7.13 (s, 1H, Ar H), 6.91 (s, 2H, Ar H), 6.77 (t, J = 6.74 Hz, 1H, Ar H), 6.55 (br. s, 2H, Ar H), 3.62 (d, J = 12.31 Hz, 1H, O C H 2 ), 3.23 (br. s, 1H, O C H 2 ), 3.07 (br. s, 2H, O C H 2 ), 2.95 (br. s, 4H, N C H 2 ), 2.28 (br. s, 2H, O C H 2 ), 2.14 (m (9), 2H, O C H 2 ), 0.98 (br. s, 8H, C H 2 C H 2 ), 0.92 (t, J = 7 .33 Hz, 4H, Ar C H 2 ). Synthesis of [3,5 CF 3 N C C C N]H(SiMe 3 ) 2 (11) To a solution of THF (2 mL) containing 4 (1.01 g, 1.72 mmol) and a stirbar, MeMgCl (1.3 mL 3 M, 3.25 mmol) in THF (2 mL) was added dropwise at 35 C. The solution was stirred at ambient tem perature for 3 h. Chlorotrimethylsilane (610 mg, 5.65 mmol) of was added at 35 C. The solution was kept at 35 C for 1 h then stirred at ambient temperature for 15 h. 1,4 dioxane (2 mL) was then added causing precipitation of MgCl 2 The solution was filtered and volatiles were removed in vacuo causing crystallization of the product. Yield 931 mg (1.27 mmol, 73.8%). 1 H NMR (300 MHz, C 6 D 6 7.40 (s, 2H, Ar H), 7.35 (s, 4H, Ar H), 7.02 (t, J = 7.61 Hz, 1H, Ar H), 6.77 (dd, J = 1.64, 7.61 Hz, 2H, Ar H), 6.68 (s, 1H, Ar H), 3.23 (t, J = 7.46

PAGE 29

29 Hz, 4H, N C H 2 ), 2.48 (t, J = 7.31 Hz, 4H, Ar C H 2 ), 0.00 (s, 18H (15H observed), SiMe 3 ). 13 C{ 1 H} NMR ( 128.39 C 6 D 6 0.74 (s, Si(CH 3 ) 3 ), 35.60 (s, CH 2 Ar), 49.00 (s, CH 2 N), 112.34 (s, aromatic), 118.74 (s, aromatic), 120.81 (s, aromatic), 122.90(s, aromatic), 129.57 (s, aromatic), 129.57 (s, aromatic), 129.91 (s, aromatic), 132.75 (q, J = 32.23 H z, CF 3 ), 140.07 (s, aromatic), 150.75 (s, aromatic). 19 F { 1 H} NMR ( C 6 D 6 63.32 (s, CF 3 ). Anal. Calcd for C 32 H 36 F 12 N 2 Si 2 : C, 52.45 ; H, 4.95 ; N, 3.82 Found: C, 52.470 ; H, 4.816; N,3.689 X ray Experimental Details F or [ 3,5 CF 3 N C C C N ]H 3 (4) Data were col lected at 173 K on a Siemens SMART PLATFORM equipped with A CCD area detector and a graphite monochromator utilizing MoK radiation ( = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collec ted using the scan method (0.3 frame width). The first 50 frames were re measured at the end of data collection to monitor instrument and crystal stability (maximum correction on I was < 1 %). Absorption corrections by integration were applied based o n measured indexed crystal faces. The structure was solved by the Direct Methods in SHELXTL6, and refined using full matrix least squares. The non H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal positions and wer e riding on their respective carbon atoms. The asymmetric unit consists of two chemically equivalent but crystallographically independent. They differ by the orientations of the side aryl rings with respect to the central one. Out of the eight CF 3 groups six of them are disordered and were refined in two parts each. A total of 890 parameters were refined in the final cycle of refinement using 10886 reflections with I > 2 (I) to yield R 1 and wR 2 of 6.33 % and 13.87 %, respectively. Refinement was done usi ng F 2

PAGE 30

30 X ray Experimental Details F or (2,6 i PrNCN)[Zr(NMe 2 ) 3 ] 2 (6) Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD area detector and a graphite monochromator utilizing MoK radiation ( = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the scan method (0.3 frame width). The first 50 frames were re measured at the end of data collection to monitor instrument and crystal stability (maximum co rrection on I was < 1 %). Absorption corrections by integration were applied based on measured indexed crystal faces. The structure was solved by the Direct Methods in SHELXTL6, and refined using full matrix least squares. The non H atoms were treated a nisotropically, whereas the hydrogen atoms were calculated in ideal positions and were riding on their respective carbon atoms. A total of 507 parameters were refined in the final cycle of refinement using 10924 reflections with I > 2 (I) to yield R 1 and wR 2 of 3.95% and 8.19%, respectively. Refinement was done using F 2 X ray Experimental Details F or [ (3,5 CF3NCCCN)Zr(NMe2)3HNMe2]2 (7) Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD area detector and a graphite monochromator utilizing MoK radiation ( = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the scan method (0.3 frame width). The first 50 frames were re measure d at the end of data collection to monitor instrument and crystal stability (maximum correction on I was < 1 %). Absorption corrections by integration were applied based on measured indexed crystal faces. The structure was solved by the Direct Methods in SHELXTL6, and refined using full matrix least squares. The non H atoms were treated anisotropically, whereas the hydrogen atoms

PAGE 31

31 were calculated in ideal positions and were riding on their respective carbon atoms. The asymmetric unit consists of a half d imer and a benzene solvent molecule. The complex had all four CF3 groups disordered and each set of three F atoms was refined in three positions with their site occupation factors dependently refined to a total of on1. All F atoms were refined with isotr opic displacement parameters. A total of 543 parameters were refined in the final cycle of refinement using 7414 reflections with I > 2 (I) to yield R 1 and wR 2 of 5.37% and 13.33%, respectively. Refinement was done using F 2 The toluene molecule were disordered and could not be modeled properly, thus program SQUEEZE, a part of the PLATON package of crystallographic software, was used to calculate the solvent disorder area and remove its contribution to the overall intensity data. X ray E xperimental D etails for [ (3,5 CF 3 N C C C N]HMg(THF) 2 (10) Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD area detector and a graphite monochromator utilizing MoK radiation ( = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the scan method (0.3 frame width). The first 50 frames were re measured at the end of data collection to m onitor instrument and crystal stability (maximum correction on I was < 1 %). Absorption corrections by integration were applied based on measured indexed crystal faces. The structure was solved by the Direct Methods in SHELXTL6, and refined using full ma trix least squares. The non H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal positions and were riding on their respective carbon atoms. Two of the four CF3 groups are disordered one in two part and the other in t hree parts. Their site occupation factors were dependently refined and their displacement parameters were treated isotropically. A

PAGE 32

32 total of 556 parameters were refined in the final cycle of refinement using 4126 reflections with I > 2 (I) to yield R 1 and wR 2 of 5.60% and 14.61%, respectively. Refinement was done using F 2 Scheme 2 1. Synthesis of ArN C C C NH 3 (where Ar = 2,4,6 MeC 6 H 3 ( 3 ) and 3,5 CF 3 C 6 H 3 ( 4 ) ) Scheme 2 2. Synthesis of 6 and 7 (where Ar = 2,4 i PrC 6 H 3 ( 6 ) and 3,5 CF 3 C 6 H 3 ( 7 )).

PAGE 33

33 Scheme 2 3. Dramatic reactivity difference between ligands 4 and 5 Synthesis of the molybdenum dinuclear species (3,5 CF 3 N C C C N)[Mo(NMe 2 ) 3 ] 2 ( 8 ). Scheme 2 4. Synthesis of the dimagnesio salt [3,5 CF 3 N C C C N]H[MgCl(THF) 2 ] 2 ( 9 ) and the minor impurity monomagnesio salt [ (3,5 CF 3 N C C C N]HMg(THF) 2 ( 10 ). Scheme 2 5. Synthesis of the bistrimethylsily l species [3,5 CF 3 N C C C N]H(SiMe 3 ) 2 ( 11 ).

PAGE 34

34 Figure 2 1. ORTEP diagram of [ 3,5 CF 3 N C C C N ]H 3 ( 4 ) Thermal ellipsoids are displayed at the 50% probability level. Hydrogen atoms and cocrystallized solvent molecules are omitted for clarity.

PAGE 35

35 Figure 2 2. ORTE P diagram of (2,6 i Pr NCN)[Zr(NMe 2 ) 3 ] 2 ( 6 ) Thermal ellipsoids are displayed at the 50% probability level. Hydrogen atoms and cocrystallized solvent molecules are omitted for clarity.

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36 Figure 2 3. ORTEP diagram of (3,5 CF 3 N C C C N)[ Zr (NMe 2 ) 2 (HNMe 2 ) ] 2 ( 7 ) Thermal ellipsoids are displayed at the 50% probability level. Hydrogen atoms and cocrystallized solvent molecules are omitted for clarity.

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37 Figure 2 4. ORTEP diagram of [ (3,5 CF 3 N C C C N]HMg(THF) 2 ( 10 ) Thermal ellipsoids are displayed at the 50 % probability level. Hydrogen atoms and cocrystallized solvent molecules are omitted for clarity.

PAGE 38

38 Figure 2 5. 1 H NMR spectra of 2,2' (1,3 phenylene)diethanamine ( 2 ) in C 6 D 6

PAGE 39

39 Figure 2 6. 1 H NMR spectra of [2,4,6 Me N C C C N ]H 3 ( 3 ) in C 6 D 6

PAGE 40

40 Fig ure 2 7. 1 H NMR spectra of [ 3,5 CF 3 N C C C N ]H 3 ( 4 ) in C 6 D 6

PAGE 41

41 Figure 2 8. 1 3 C{ 1 H } NMR spectrum of [ 3,5 CF 3 N C C C N ]H 3 ( 4 ) in C 6 D 6

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42 Figure 2 9. 1 H NMR spectra of [ (3,5 CF 3 N C C C N)Zr(NMe 2 ) 3 HNMe 2 ] 2 ( 7 ) in C 6 D 6

PAGE 43

43 Figure 2 10. 1 3 C{ 1 H } NMR spectrum of [ (3,5 CF 3 N C C C N)Zr(NMe 2 ) 3 HNMe 2 ] 2 ( 7 ) in THF d 8

PAGE 44

44 Figure 2 11. 1 H NMR spectra of (3,5 CF 3 N C C C N)[Mo(NMe 2 ) 3 ] 2 ( 8 ) in C 6 D 6

PAGE 45

45 Figure 2 12. 1 3 C{ 1 H } NMR spectrum of (3,5 CF 3 N C C C N)[Mo(NMe 2 ) 3 ] 2 ( 8 ) in C 6 D 6

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46 Figure 2 13. 1 H NMR spectra of [3,5 CF 3 N C C C N]HMg(THF ) 2 ( 10 ) in Tol d 8 @ 75 C.

PAGE 47

47 Figure 2 14. 1 H NMR spectra of [3,5 CF 3 N C C C N]H(SiMe 3 ) 2 ( 11 ) in C 6 D 6

PAGE 48

48 Figure 2 15. 1 3 C{ 1 H } NMR spectrum of [3,5 CF 3 N C C C N]H(SiMe 3 ) 2 ( 11 ) in C 6 D 6

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49 Figure 2 16. 19 F NMR spectrum of [3,5 CF 3 N C C C N]H(SiMe 3 ) 2 ( 11 ) in C 6 D 6

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50 Tab le 2 1. Selected angles and bond lengths for crystal structures 6 7 and 10 (2,6 i Pr NCN)[Zr(NMe 2 ) 3 ] 2 ( 6 ) (3,5 CF 3 N C C C N)[ Zr (NMe 2 ) 2 (HNMe 2 ) ] 2 ( 7 ) [ (3,5 CF 3 N C C C N]HMg(THF) 2 ( 10 ) Bond Lengths () Zr N1 2.137(2) Zr N4 2.036(3) Mg O2 2.0140(18) Zr N2 2.212(2) Zr N5 2.037(3) Mg N1 2.019(2) Zr N4 2.036(3) Zr N1 2.137(2) Mg N2 2.026(2) Zr N5 2.037(3) Zr N2 2.212(2) Mg O1 2.0491(18) Zr N3 2.461(3) Zr N3 2.461(3) Zr N6 2.046(3) Zr N7 2.030(3) Zr N8 2.034(3) Bond Angles (deg) N4 Zr1 N5 110.96(10) N4 Zr N5 114.44(11) O2 Mg N1 11 0.69(8) N4 Zr1 N3 105.44(10) N4 Zr N1 122.10(10) O2 Mg N2 103.98(8) N5 Zr1 N3 107.72(11) N5 Zr N1 121.45(10) N1 Mg N2 130.58(9) N4 Zr1 N1 108.41(10) N4 Zr N2 96.60(10) O2 Mg O1 100.77(8) N5 Zr1 N1 114.12(10) N5 Zr N2 95.28(10) N1 Mg O1 103.00(8) N3 Zr1 N1 109.82(10) N1 Zr N2 92.44(9) N2 Mg O1 103.86(8) N7 Zr2 N8 108.84(11) N4 Zr N3 85.90(11) N7 Zr2 N6 105.30(11) N5 Zr N3 88.61(11) N8 Zr2 N6 108.31(11) N1 Zr N3 81.62(10) N7 Zr2 N2 114.06(10) N2 Zr N3 174.00(10) N8 Zr2 N2 108 .74(10) N6 Zr2 N2 111.40(10)

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51 Table 2 2. Crystal data, structure solution and refinement for [ 3,5 CF 3 N C C C N ]H 3 ( 4 ) identification code (ac04) empirical formula C 26 H 20 F 12 N 2 formula weight 588.44 T (K) 173(2) ( ) 0.71073 crystal syste m Triclinic space group P 1 a ( ) 11.9159(14) b ( ) 14.003(2) c ( ) 16.6156(18) (deg) 75.343(2) (deg) 71.727(2) (deg) 74.212(2) V ( 3 ) 2490.3(5) Z 4 calcd (Mg mm 3 ) 1.570 abs coeff (mm 1 ) 0.156 F (000) 1192 crystal size (mm 3 ) 0.11 x 0 .08 x 0.05 range for data collection 1.31 to 22.50 limiting indices no. of reflns coll cd 10886 no. of ind reflns ( R int ) 6488 [R(int) = 0.1286] completeness to = 22.50 99.8 % absorption corr Integration r efinement method Full matrix least squares on F 2 data / restraints / parameters 6488 / 0 / 890 GOF c on F 2 0.896 R 1, a wR 2 b [I > 2 ] 0.0633, 0.1387 [3149] R 1, a wR 2 b (all data) 0.1350, 0.1701 largest diff. peak and hole 0.310 and 0.263 e. 3 R1 = (||F o | |F c ||) / |F o | w R2 = [ w(F o 2 F c 2 ) 2 ] / w F o 2 2 ]] 1/2 S = [ w(F o 2 F c 2 ) 2 ] / (n p)] 1/2 w= 1/[ 2 (F o 2 )+(m*p) 2 +n*p] p = [max(F o 2 ,0)+ 2* F c 2 ]/3, m & n are constants.

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52 Table 2 3. Crystal data and structure refinement for (2,6 i PrNCN)[Zr(NMe 2 ) 3 ] 2 ( 6 ) identification code ( kv13 ) empirical formula C 44 H 78 N 8 Zr 2 formula weight 901.58 T (K) 173(2) ( ) 0.71073 crystal system Monoclinic space group P2 1 /n a ( ) 9.5540(4) b ( ) 19.4781(9) c ( ) 26.2784(12) (deg) 90 (deg) 98.343(1) (deg) 90 V ( 3 ) 4838. 5(4) Z 4 calcd (Mg mm 3 ) 1.238 abs coeff (mm 1 ) 0.467 F (000) 1912 crystal size (mm 3 ) 0.18 x 0.10 x 0.09 range for data collection 1.57 to 27.50 limiting indices no. of reflns coll cd 30297 no. of ind reflns ( R int ) 10924 [R(int) = 0.0661] completeness to = 22.50 98.3 % absorption corr Integration r efinement method Full matrix least squares on F 2 data / restraints / parameters 10924 / 0 / 507 GOF c on F 2 0.854 R 1, a wR 2 b [I > 2 ] 0.0395, 0.0819 [5881] R 1, a wR 2 b (all data) 0.0884, 0.0879 largest diff. peak and hole 0.593 and 0.778 e. 3 R1 = (||F o | |F c ||) / |F o | wR2 = [ w(F o 2 F c 2 ) 2 ] / w F o 2 2 ]] 1/2 S = [ w(F o 2 F c 2 ) 2 ] / (n p)] 1/2 w= 1/[ 2 (F o 2 )+(m*p) 2 +n*p] p = [max(F o 2 ,0)+ 2* F c 2 ]/3, m & n are constants.

PAGE 53

53 Table 2 4. Crystal data and structure refinement for [ (3,5 CF 3 N C C C N)Zr(NMe 2 ) 3 HNMe 2 ] 2 ( 7 ) i dentification code (ac03) empirical formula C 76 H 86 F 24 N 10 Zr 2 formula weight 1777.99 T (K) 173(2) ( ) 0.71073 crystal system Triclinic space group P 1 a ( ) 9.1226(5) b ( ) 12.3882(7) c ( ) 18.5955(10) (deg) 77.615(1) (deg) 79.183(1 ) (deg) 88.269(1) V ( 3 ) 2016.04(19) Z 1 calcd (Mg mm 3 ) 1.464 abs coeff (mm 1 ) 0.362 F (000) 908 crystal size (mm 3 ) 0.19 x 0.19 x 0.06 range for data collection 1.68 to 27.50 limiting indices no. of reflns coll cd 13079 no. of ind reflns ( R int ) 8784 [R(int) = 0.0386] completeness to = 22.50 94.9 % absorption corr Integration r efinement method Full matrix least squares on F 2 data / restraints / parameters 8784 / 4 / 543 GOF c on F 2 1.048 R 1, a wR 2 b [I > 2 ] 0.0537, 0.1333 [7414] R 1, a wR 2 b (all data) 0.0638, 0.1398 largest diff. peak and hole 0.902 and 0.778 e. 3 R1 = (||F o | |F c ||) / |F o | wR2 = [ w(F o 2 F c 2 ) 2 ] / w F o 2 2 ]] 1/2 S = [ w(F o 2 F c 2 ) 2 ] / (n p)] 1/2 w= 1/[ 2 (F o 2 )+(m*p) 2 +n*p] p = [max(F o 2 ,0)+ 2* F c 2 ]/3, m & n are constants.

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54 Table 2 5. Crystal data and structure refinement for [ (3,5 CF 3 N C C C N]HMg(THF) 2 ( 10 ) identificat ion code (ac11) empirical formula C 39 H 46 F 12 Mg N 2 O 2 formula weight 827.09 T (K) 173(2) ( ) 0.71073 crystal system Monoclinic space group P2 1 /c a ( ) 17.9480(12) b ( ) 9.5720(7) c ( ) 24.8666(17) (deg) 90 (deg) 110.180(1) (deg) 90 V ( 3 ) 4009.8(5) Z 4 calcd (Mg mm 3 ) 1.370 abs coeff (mm 1 ) 0.136 F (000) 1720 crystal size (mm 3 ) 0.19 x 0.15 x 0.08 range for data collection 1.74 to 27.50 limiting indices no. of reflns coll cd 26429 no. of ind reflns ( R int ) 9163 [R(int) = 0.0811] completeness to = 22.50 99.4 % absorption corr Integration r efinement method Full matrix least squares on F 2 data / restraints / parameters 9163 / 1 / 556 GOF c on F 2 0.862 R 1, a wR 2 b [I > 2 ] 0.0560, 0.1461 [4126] R 1, a wR 2 b (all data) 0.1284, 0.1636 largest diff. peak and hole 0.416 and 0.317 e. 3 R1 = (||F o | |F c ||) / |F o | wR2 = [ w(F o 2 F c 2 ) 2 ] / w F o 2 2 ]] 1/2 S = [ w(F o 2 F c 2 ) 2 ] / (n p)] 1/2 w= 1/[ 2 (F o 2 )+(m*p) 2 +n*p] p = [max(F o 2 ,0)+ 2* F c 2 ]/3, m & n are constants.

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55 CHAPTER 3 SYNTHESIS AND REACTIVITY OF TERPHENYL OCO 3 PINCER COMPLEXES Synthesis and C haracterizati on of T erphenyl [ t BuOCO]H 3 (17) Alkoxides react readily with metal amides, owing to the greater affinity of early transition metals for oxygen than for nitrogen. 35 ,3 6 Thus, an OCO 3 pincer format ( 17 ) should effect an increase in reactivity and stability with early transition metals. The alkyl groups must be of sufficient size to prevent metal metal bonds from forming as well as imparting protection to the active site during reactions. 3 7 The terphenyl framework also imparts greater rigidity to the pincer backbone over the previous N C C C N design. The synthesis of the terphenyl OCO ligand 17 is a five step sequence ( Scheme 3 1 ) starting with selective ortho bromination of 2 tert butylphenol ( 12 ) to give bromophenol 13 Phenol 1 3 is then masked as its methy l ether, and the Grignard derivative of 1 4 is generated by treatment with magnesium metal Dibromoiodide 1 5 is easily made from 2,6 dibromoaniline via diazotization, and is alkylated with 1 4 The bismethyl ether 16 is then deprotected by treatment with b oron tribromide. Purification by flash column chromatography affords diol 17 as a white solid in 21% yield from 12 ( Scheme 3 1 ). The identity of 17 was verified by 1 H NMR, 13 C NMR spectrometry and HRMS. The 1 H NMR spectrum revealed the expected, single t from two tert butyl groups that integrate to 18 protons at 1.44 ppm and two OH protons at 7.14 ppm. A 13 C NMR spectrum of 17 shows the 10 signals in the aromatic region with two signals at 35.541 and 30.279 ppm assigned to the carbons of the t Bu groups. The calculated mass for 17 is 374.2240 amu and was experimentally found to be 374.2209 amu, confirming the identity of 17 as the desired terphenyl diol.

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56 Synthesis and C haracterization of [ t BuOCO] MoNMe 2 (HNMe 2 ) 2 (18) Diol 17 was treated with purple Mo(NMe 2 ) 4 in pentane at 35 C ( Scheme 3 2 ) As the reaction warms an orange powder precipitates out of solution in 80% yield. Transparent orange crystals were grown at 35 C from DME over a period of two days. The broadened peaks in the 1 H NMR spectrum are characteristic of a paramagnetic Mo(IV) bearing two unpaired electrons. The t Bu groups are visible as a singlet that is shifted from 1.44 ppm in the free ligand to 2.82 ppm upon coordination to Mo. Singlets at 1.73 and 8.72 ppm are attributed to the pa ir of methyl groups on the coordinated amide. The methyl protons on the amines appear as singlets at 3.45 and 1.98 ppm, with the NH proton at 3.26 ppm. The ligand contributes 6e to the metal and another 6e are donated from the amide and two amines. An additional 4e bonding orbitals from the nitrogen and oxygen lone pairs. Considering the additional 2e from the metal, 1 8 is an 18e complex. The structure of 18 was determined by single crystal X ray crystallography and the molecular structure is presented in Figure 3 1 Clearly 1 7 is bound in a terdendate fashion to molybdenum with a dimethylamine in the position trans to the ipso carbon of the backbone and the remaining axial pos i tions are occupied by coordinated dimethylamine and dimethyla mide ligands As expected with molybdenum alkoxide compounds generated from Mo(NMe 2 ) 4 dimethylamine remains in the coordination sphere. 38 The amido and amine ligands are easily distinguished since N1 is trigonal whereas N2 and N3 are pyramidal. In addi tion the M N bond lengths are significantly different ( Table 3 1 ) The Mo NMe 2 ligand is twisted away from the N2 Mo N3 plane by 35 to break the otherwise perfect solid state C s symmetry. A space filling model indicates the twist is due to packing force s that place a DME solvent molecule atop the amido group. Considerable strain is imparted to the pincer backbone and is attributable to congestion caused by the dimethylamine

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57 ligand trans to C1. The N Me groups are nearly parallel to the O1 C1 O2 plane which forces them into the t As a result, the t Bu groups are strained, creating 33 and 32 torsion angles between the aryl backbone C2 C7 and C6 C17 connections, respectively, and the central ring is bent up by 30. Synthesis and C ha racterization of [ t Bu OCO ]MoCl (1 9 ) To derivatize the complex such that it would be more amenable to salt metathesis, 1 8 was treated with 3 equiv of lutidine hydrochloride in pentane. 39 Three equivalents were required due to the insolubility of lutidine h ydrochloride in pentane ( Scheme 3 3 ). This reaction results in protonation of the remaining amide and installs a chloride trans to the M C bond. The remaining HCl salts were removed from the resulting red powder by filtration. The 1 H NMR spectrum of 19 revealed broadened resonances indicative of a paramagnetic complex. The t Bu protons of the ligand appear at 1.37 ppm and the coordinated dimethyl amine protons have shifted upfield to 2.02 ppm. Complex 1 9 was crystallized from benzene as single crystal s up to 5 mm across, which allowed for the structure to be determined by X ray crystallography. X ray structure analysis shows the strain observed in the previous structure 18 is relieved, as the ligand has acquired a 33 twist in the backbone along the C l1 Mo C1 axis thus imparting 1 9 C 2 symmetry ( Figure 3 2 ). The octahedral Mo(IV) center is coordinated by the pincer ligand, trans dimethyl amines, and a chloride. The coordinated dimethylamine s orient off axis by 57 and are rotated 88 with respect to e ach other, which, again, can be attri buted to sterics. The O1 Mo angle has decreased slightly from 166.45 in 1 8 to 165.3 2 ( Table 3 1 ). The chemistry of 19 was probed and it was determined that t he dimethyl amines on 1 9 are bound tightly and do not release under vacuum nor substitute with THF, DME or CO, even at

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58 elevated temperatures (80 C). In addition t he complex is stable for short periods when exposed to air. Conclusions Development of new trianionic pincer ligands is two fold. While new l igand designs need to be explored, successful routes to installing these new ligands on metals need to be developed. Stepwise modifications of our original NCN format led to straightforward metallation of molybdenum using an OCO pincer ligand. While the terdentate behavior of an OCO ligand has now been established with molybdenum, metallation will require modification, possibly to utilize molybdenum chlorides as reagents. Alternative metallation routes will avoid coordinated dimethylamines which have pr oven difficult to remove and can impede further reactivity. Formation of aryloxide alkali salts 4 0 and aryl ethers 4 1 are established and can provide insight into alternative metallation routes with 17 Our previous work exploring reactivity of early trans ition metals will also aid in this research. Established synthetic routes to our ligands are easily modified to incorporate new designs quickly as needed. The research presented here will provide a solid foundation for future development of trianionic pi ncer ligands. Experimental General Considerations Unless specified otherwise, all manipulations were performed under an inert atmosphere using standard Schlenk or glovebox techniques. Pentane, hexanes, toluene, diethyl ether, tetrahydrofuran, and 1,2 dimet hoxyethane were dried using a GlassContour drying column. C 6 D 6 and toluene d 8 (Cambridge Isotopes) were dried over sodium benzophenone ketyl, distilled or vacuum transferred and stored over 4 molecular sieves. THF d 8 and acetone d 6 (Cambridge Isotopes) was stored over 4 sieves and used without further purification.

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59 NMR spectra were obtained on Gemini (300 MHz), VXR (300 MHz), or Mercury (300 MHz) 1 H and 13 C NMR spectra, the residual protio o r carbon solvent peak were referenced as an internal reference. GC/MS spectra were recorded on an Agilent 6210 TOF MS instrument. C, H, and N elemental analysis were determined by Robertson Microlit Laboratories Inc. and Complete Analysis Laboratories. Sy nthesis of 2 bromo 6 tert butylphenol ( 13 ) This compound was made according to the procedure Zhang et al 4 2 Purification was achieved by flash column chromatography (3:1 pentane;CHCl 3 ) to give 13 as a clear colorless oil in 81% yield. 1 H NMR and 13 C NMR were consistent with those previously reported. Synthesis of 1 bromo 3 tert butyl 2 methoxybenzene ( 14 ) To a solution of 1 3 (6.06 g, 26 mmol) in DMF (30mL) was added K 2 CO 3 (5.5 g, 1.5 equiv., 40 mmol) and MeI (2.5 mL, 1.5 equiv., 40 mmol). The resulting mixture was stirred at ambient tempera ture for 16 h. Water was added and the mixture was extracted (2X) with Et 2 O. The combined organic extracts were washed successively with water, saturated Na 2 S 2 O 3 and brine, dried over MgSO 4 filtered and concentrate d in vacuo to a yellow oil. Methyl ether 14 was obtained by vacuum distillation (58 60 C @ 4 mTorr) as a white crystalline solid (5.76g. 90% yield). 1 H NMR (300 MHz, DMSO d6) 7.47 (dd, 3 J = 8.1 Hz, 4 J = 1.5 Hz, 1H), 7.29 (dd, 3 J = 8.1 Hz, 4 J = 1.5 Hz, 1 H), 6.97 (dd, J = J = 8.1 Hz, 1H), 3.83 (s, OC H 3, 3H), 1.33 (s, tBu, 9H); 13 C NMR DMSO d6) 30.6 [C( C H3)3], 35.1 [ C (CH3)], 61.1 (O C H3), 117.4 ( C Br), 125.0 (=H C CH CBr), 126.6 (tBu C H), 131.9 (= C H CBr), 144.7 ( C t Bu), 156.1 ( C OMe); HRMS (GC E1 found) for C 11 H 15 BrO (M + ) 242.0301 (242.0286).

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60 Synthesis of 1,3 dibromo 2 iodobenzene ( 15 ) This compound was made according to the procedure of Hart and coworkers. 4 3 The compound was recrystallized from isopropano before use. 1 H and 13 C NMR were consis tent with those previously reported. Synthesis of di tert butyl dimethoxy terphenyl ( 16 ) This compound was made following the general procedure of Hart and coworkers. 4 3 To a solution of 2 (4.84 g, 3.5 equiv., 20 mmol) in dry THF (40 m L) was added Mg turnings (540 mg, 3.9 equiv., 22 mmol). The resulting mixture was heated to reflux for an additional 1 h. A solution of 3 (2.06 g, 1 equiv., 5.7 mmol) in dry THF (20 mL) was added dropwise over 1 h to the reaction mixture. The resulting m ixture was heated at reflux for 16 h. The mixture was cooled to room temperature, and was quenched with 6N HCl. The mixture was extracted with Et 2 O (3 x 20 mL). The combined organix extracts were washed with saturated Na 2 S 2 O 3 and brine, dried over MgSO 4 filtered and concentrated in vacuo to a brown oil. Terphenyl 16 was obtained via flash column chromatography (8:1 hexanes:CHCl 3 ) as a white solid (1.3 g, 57% yield). 1 H NMR (300 MHz, C 6 D 6 13 C NMR (C 6 D 6 ) 31.5 [C(CH3)3], 35.7 [C(CH3)3], 60.7 (OCH3) 124.2 (C ), 127.0 (C ), 128.4 (C ), 129.3 (C ), 130.5 (C ), 130.7 (C ), 136.1 (C ), 141.2 (C ), 143.6 (C ), 158.4 (C ); HRMS (DIP C1 for C 28 H 34 O 2 (M + ) 402.2553 (402.2536). Synthesis of di tert butyl terphenyl diol ([ t BuOCO]H 3 ) ( 17 ) To a solution of 16 (1.3 g, 3.2 mmol) in CH 2 Cl 2 (20 mL) at 0 C was added BBr 3 (1.6 mL, 5 equiv., 16 mmol). The mixture was warmed slowly to room temperature over 6 h. MeOH was added to quench the reaction, and the mixture was concentrated under reduced pressure. Diol 17 was obtained by flash column chromatography of the residue (5:1 pentane:CHCl 3 ) as a white

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61 solid (600 mg, 50% yield). 1 H NMR (300 MHz, acetone d 6 7.58 (dd, J = J = 7. 8 Hz, 1H, H ), 7.54 (dd, J = J = 1.8 Hz, 1H, H ), 7.38 (dd, 3 J = 7.8 Hz, 4 J = 1.8 Hz, H ), 7.28 (dd, 3 J = 8.1 Hz, 4 J = 1.8 Hz, 2H), 7.14 (s, 2 H, OH), 7.07 (dd, 3 J = 8.1 Hz, 4 J = 1.8 Hz, 2H), 6.89 (dd, J = J = 8.1 Hz, 2H, H ), 1.44 (s, 18H, t Bu); 13 C NMR (C 6 D 6 30.3 [C( C H 3 ) 3 ], 35.5 [ C (CH 3 ) 3 ], 121.0 (C ), 127.7 (C ), 128.8 (C ), 129.0 (C ), 129.1 (C ), 130.7 (C ), 131.5 (C 5 ), 137.0 (C ), 139.6 (C ), 151.7 (C ); HRMS (DIP C1 26 H 30 O 2 (M + ) 374 .2240 (374.2209). Synthesis of [ t BuOCO ] MoNMe 2 (HNMe 2 ) 2 (18) To a solution of [ t Bu OCO ]H 3 ligand ( 17 ) (500 mg, 1.34 mmol) in pentane (2 mL) Mo(NMe 2 ) 4 (218mg, 1 equiv., 1.34 mmol) in pentane (2 mL) was added quickly at 35 C. The resulting brown slurry was s tirred with a spatula until it was warmed to room temperature. The orange precipitate was filtered off, washed with cold pentane and dried in vacuo The product ( [3,3'' di tert butyl 2,2'' di(hydroxy 1,1':3',1'' terphenyl 2' yl N methylmethanam inato)bis( N me thylmethanamine)molybdenum(IV)) ) ( 18 ) was recrystallized from DME as dark orange crystals at ; Yield 642mg (1.07 mmol, 80%) 1 H NMR (300 MHz, THF D 8 9.61 (br. s, 2H Ar H), 3.78 (s, 2H, Ar H ), 3.45 (br. s, 3H, NH(C H 3 ) 2 ), 3.26 (s, 1H, N H (CH 3 ) 2 ), 3.17 (s, 1H, Ar H), 2.82 (s, 18H, C(C H 3 ) 3 ), 2.14 (s, 2H, Ar Hs), 1.98 (br. s, 9H, NH(C H 3 ) 2 ), 1.73 (s, 3H, N(C H 3 ) 2 ), 8.72 (s, 3H, N(C H 3 ) 2 ). 13 C{ 1 H} NMR ( 67.57 Hz, THF D 8 29.76 (s, C, aromatic), 40.55 (s, CH, aromatic), 43.77 (s, N ( C H3)2), 47.28 (s, CH, aromatic), 49.08 (s, C( C H 3 ) 3 ), 58.31 (s, C (CH 3 ) 3 ), 72.02 (s, CH, aromatic), 79.92 (br. s, C, aromatic), 164 (br. s, C O, aromatic). Anal. Calcd for C 32 H 47 MoN 3 O 2 C, 63.88; H, 7.87; N, 6.98. Found C, 61.13; H, 6.90; N,3.63.

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62 Synthesi s of [ t BuOCO ] Mo (HNMe 2 ) 2 Cl (19) To a solution of [ t BuOCO]Mo(NMe 2 )(HNMe 2 ) 2 ( 18 ) (250 mg, 0.415 mmol) in pentane (2 mL) was added lutidine HCl (180 mg, 3 equiv., 1.260 mmol). Afte r vigorous stirring for 12 h all volatiles were removed in vacuo and the remai ning solid was dissolved in THF (2 mL). Remaining lutidine HCl salts were filtered off with a medium porosity fritted funnel. Volatiles from the filtrate were removed in vacuo and the remaining solid was triturated with pentane to yield OCO t BuMo (HNMe 2 ) Cl ( 19 ) as a dark red powder. The product was recrystallized from benzene as dark red crystals; Yield 99 mg (0.167 mmol, 40%) 1 H NMR (300 MHz, C 6 D 6 29.40 (s, 2H, Ar H ), 3.57 (br s, 1H, Ar H), 2.42 (s, 2H, Ar H), 1.55 (s, 2H, Ar H ), 1.37 (s, 18H, C (C H 3 ) 3 ), 1.40 (s, 3H, NH (C H 3 ) 2 ), 2.02 (s, 3H, NH (C H 3 ) 2 ), 2.25 (br s, 9H, N H (C H 3 ) 2 ), 5.32 (s, 2H, Ar Hs). 13 C{ 1 H} NMR ( 67.57 Hz, THF D 8 30.20 (s, NH ( C H 3 ) 2 ), 41.24 (s, C( C H 3 ) 3 ), 44.95 (s, C (CH 3 ) 3 ), 128.93 (s, CH, aromatic), 129.08 (s, CH, aromatic), 129.44 (s, CH, aromatic), 163.11 (s, CH, aromatic), 173.11 (s, CH, aromatic). Anal. Calcd for C 42 H 41 D 12 ClMoN 2 O 2 (2 C 6 D 6 ) C, 66.22; H, 6 .96; N,3.68. Found: C,66.03; H,7.05; N,3.72. X ray Experimental Details F or [ t BuOCO ] MoNMe 2 (HNMe 2 ) 2 (18) Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD area detector and a graphite monochromator utilizing MoK radiation ( = 0. 71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the scan method (0.3 frame width). The first 50 frames were re measured at the end of data collection to monitor instrument a nd crystal stability (maximum correction on I was < 1 %). Absorption corrections by integration were applied based on measured indexed crystal faces.

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63 The structure was solved by the Direct Methods in SHELXTL6, and refined using full matrix least squares. The non H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal positions and were riding on their respective carbon atoms. In addition to the complex, there is a dme molecule in the asymmetric unit. The protons, H1 and H2, on N1 and N2 respectively, were obtained from a Difference Fourier map and refined without any constraints. A total of 405 parameters were refined in the final cycle of refinement using 5629 reflections with I > 2 (I) to yield R 1 and wR 2 of 4.77 % and 9.57 %, respectively. Refinement was done using F 2 X ray Experimental Details F or [ t BuOCO] Mo(HNMe 2 ) 2 Cl (19) Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD area detector and a graphite monochromator utilizing MoK radiation ( = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the scan method (0.3 frame width). The first 50 frames were re measured at the end of data collection to monitor instru ment and crystal stability (maximum correction on I was < 1 %). Absorption corrections by integration were applied based on measured indexed crystal faces. The structure was solved by the Direct Methods in SHELXTL6, and refined using full matrix least sq uares. The non H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal positions and were riding on their respective carbon atoms. The asymmetric unit consists of a half complex and a benzene molecule of crystallization. The N proton was located in a Difference Fourier map and refined freely. The complexes are located on 2 fold rotation axes of symmetry. A total of 223 parameters were refined in the final cycle of

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64 refinement using 3320 reflections with I > 2 (I) to yiel d R 1 and wR 2 of 2.63 % and 7.71 %, respectively. Refinement was done using F 2 Scheme 3 1. Synthesis of [ t BuOCO]H 3 ( 17 ). Scheme 3 2. Synthesis of [ t BuOCO ] MoNMe 2 (HNMe 2 ) 2 ( 18 ).

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65 Scheme 3 3. Synthesis of [ t Bu TP] Mo (HNMe 2 ) 2 Cl ( 19 ). Figure 3 1. ORTEP diagram of [ t BuOCO ] MoNMe 2 (HNMe 2 ) 2 ( 18 ). Thermal ellipsoids are displayed at the 50% probability level. Hydrogen atoms and cocrystallized solvent molecules ar e omitted for clarity.

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66 Figure 3 2. ORTEP diagram of [ t BuOCO ] Mo (HNMe 2 ) 2 Cl ( 19 ). Thermal ellipsoids are displayed at the 50% probability level. Hydrogen atoms and cocrystallized solvent molecules are omitted for clarity.

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67 Figure 3 3. 1 H NMR spectr um of [ t BuOCO] H 3 ( 17 ) in acetone d 6

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68 Figure 3 4. 13 C NMR spectrum of [ t BuOCO] H 3 ( 17 ) in C 6 D 6

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69 Figure 3 5. 1 H NMR spectrum of [ t BuOCO] MoNMe 2 (HNMe 2 ) 2 ( 18 ) in THF d 8

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70 Figure 3 6. 13 C NMR spectrum of [ t BuOCO] MoNMe 2 (HNMe 2 ) 2 ( 18 ) in THF d 8

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71 Figure 3 7 1 H NMR spectrum of [ t BuOCO] Mo(HNMe 2 ) 2 Cl ( 19 ) in C 6 D 6

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72 Figure 3 8. 13 C NMR spectrum of [ t BuOCO] Mo(HNMe 2 ) 2 Cl ( 19 ) in THF d 8

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73 Table 3 1. Selected angles and bond lengths for crystal structures 18 and 19 [ t BuOCO] MoNMe 2 (HNMe 2 ) 2 ( 18 ) [ t BuOCO] Mo(HNMe 2 ) 2 C l ( 19 ) Bond Lengths () Mo1 N1 1.928(3) Mo1 O1 1.9405(11) Mo1 O1 1.997(2) Mo1 C1 2.120(2) Mo1 O2 2.014(2) Mo1 N1 2.2245(16) Mo1 C1 2.114(3) Mo1 Cl1 2.4829(6) Mo1 N2 2.390(3) Mo1 N3 2.430(3) Bond Angles (d eg) N1 Mo1 O1 98.89(11) O1 Mo1 C1 82.66(3) N1 Mo1 O2 94.58(10) O1 Mo1 N1 83.24(5) O1 Mo1 O2 166.45(9) C1 Mo1 N1 94.55(4) N1 Mo1 C1 98.88(12) O1 Mo1 Cl1 97.34(3) O1 Mo1 C1 90.35(11) C1 Mo1 Cl1 180.0 O2 Mo1 C1 89.05(11) N1 Mo1 Cl1 8 5.45(4) N1 Mo1 N2 173.45(12) C6 O1 Mo1 128.73(10) O1 Mo1 N2 83.68(10) O1 Mo1 162.32(6) C22 O2 Mo1 128.7(2) N1 Mo1 170.90(8) O2 Mo1 N2 82.77(9) C1 Mo1 N2 87.10(12) N1 Mo1 N3 92.35(12) O1 Mo1 N3 89.71(10) O2 Mo1 N3 88.23(1 0) C1 Mo1 N3 168.62(12) N2 Mo1 N3 81.60(12) C12 O1 Mo1 129.5(2)

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74 Table 3 2. Crystal data and structure refinement for [ t BuOCO] MoNMe 2 (HNMe 2 ) 2 ( 18 ) identification code (ac20) empirical formula C 36 H 57 Mo N 3 O 4 formula weight 691.79 T (K) 173(2) ( ) 0.71073 crystal system Triclinic space group P 1 a ( ) 8.5921(10) b ( ) 11.8394(14) c ( ) 18.796(2) (deg) 69.916(2) (deg) 89.349(2) (deg) 87.278(2) V ( 3 ) 1793.7(4) Z 2 calcd (Mg mm 3 ) 1.281 abs coeff (mm 1 ) 0.406 F (0 00) 736 crystal size (mm 3 ) 0.15 x 0.08 x 0. 02 range for data collection 1.08 to 27.50 limiting indices no. of reflns coll cd 12358 no. of ind reflns ( R int ) 8062 [R(int) = 0.0364] completeness to = 22.50 97.8 % abs orption corr Integration r efinement method Full matrix least squares on F 2 data / restraints / parameters 8062 / 0 / 405 GOF c on F 2 0.964 R 1, a wR 2 b [I > 2 ] 0.0477, 0.0957 [5629] R 1, a wR 2 b (all data) 0.0772, 0.1090 largest diff. peak and hole 0.723 a nd 0.490 e. 3 R1 = (||F o | |F c ||) / |F o | wR2 = [ w(F o 2 F c 2 ) 2 ] / w F o 2 2 ]] 1/2 S = [ w(F o 2 F c 2 ) 2 ] / (n p)] 1/2 w= 1/[ 2 (F o 2 )+(m*p) 2 +n*p] p = [max(F o 2 ,0)+ 2* F c 2 ]/3, m & n are constants.

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75 Table 3 3. Crystal data and structure refinement for [ t BuOCO] Mo(HNMe 2 ) 2 Cl ( 19 ) identification code (ac12) empirical formula C 42 H 53 Cl Mo N 2 O 2 formula weight 749.25 T (K) 173(2) ( ) 0.71073 crystal system Orthorhombic space group Pbcn a ( ) 10. 4875(8) b ( ) 17.2088(13) c ( ) 21.1554(15) (deg) 90 (deg) 90 (deg) 90 V ( 3 ) 3818.1(5) Z 4 calcd (Mg mm 3 ) 1.303 abs coeff (mm 1 ) 0.450 F (000) 1576 crystal size (mm 3 ) 0.15 x 0.08 x 0.08 range for data collection 1.93 to 27. 49 limiting indices no. of reflns coll cd 24328 no. of ind reflns ( R int ) 4392 [R(int) = 0.0493] completeness to = 22.50 99.9 % absorption corr Integration r efinement method Full matrix least squares on F 2 data / restraints / parameters 4392 / 0 / 223 GOF c on F 2 1.241 R 1, a wR 2 b [I > 2 ] 0.0263, 0.0771 [3320] R 1, a wR 2 b (all data) 0.0386, 0.0804 l argest diff. peak and hole 0.331 and 0.380 e. 3 R1 = (||F o | |F c ||) / |F o | wR2 = [ w(F o 2 F c 2 ) 2 ] / w F o 2 2 ]] 1/2 S = [ w(F o 2 F c 2 ) 2 ] / (n p)] 1/2 w= 1/[ 2 (F o 2 )+(m*p) 2 +n*p] p = [max(F o 2 ,0)+ 2* F c 2 ]/3, m & n are constants.

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76 LIST OF REFERENCES 1 ) Errington, R. J.; Shaw, B. L. J. Organomet. Chem. 1982 238 319 325. 2) Cr ocker, C.; Empsall, H. D.; Errington, R. J.; Hyde, E. M.; McDonald, W. S.; Markham, R.; Norton, M. C.; Shaw, B. L.; Weeks, B. J. Chem. Soc., Dalton Trans. 1982 7 1217 1224. 3) Shaw. B. L.; Errington, J.; McDonald, W. S. J. Chem. Soc., Dalton Trans. 198 0 2312 2314. 4) Shaw, B. L.; Crocker, C.; Errington, R. J.; McDonald, W. S.; Odell, K. J.; Goodfellow, R. J. J. Chem. Soc., Chem. Commun. 1979 498 499. 5) Shaw, B. L.; Moulton, C. J. J. Chem. Soc., Dalton Trans 1976 1020 1024. 6) Slagt, M. Q.; van Zwieten, D. A. P.; Moerkerk, A.; Gebbink, R.; van Koten, G. Coord. Chem. Rev. 2004 248 2275 2282. 7 ) Slagt, M. Q.; Rodrguez, G.; Grutters, M. M. P.; Gebbink, R. J. M. K.; Klopper, W.; Jenneskens, L. W.; Lutz, M.; Spek, A. L.; van Kot en, G. C hem. Eur. J. 2004 10 1331 1344. 8 ) van der Boom, M. E.; Milstein, D. Chem. Rev 2003 103 1759 1792. 9 ) Beletskaya, I. P.; Cheprakov, A. V. J. Organomet. Chem. 2004 689 4055 4082. 10 ) Albrecht, M.; van Koten, G. Angew. Chem., Int. Ed 20 01 40 3750 3781. 11) Steenwinkel, P.; Gossage, R. A.; van Koten, G. Chem. Eur. J 1998 4 759 762. 12 ) Rierveld, M. H. P.; Grove, D. M.; van Koten, G. New. J. Chem 1997 21 (6 7), 751 771. 13) Albrecht, M.; Kocks, B. M.;Spek, A. L.; van Koten, G J. Organomet. Chem. 2001 624 (1 2) 271 286. 1 4 ) van der Boom, M. E.; Milstein, D. Chem. Rev. 2003 103 1759 1792. 1 5 ) Slagt, M. Q.; Rodrgues, G.; Grutters, M. M. P.; Gebbink, R.J. M. K.; Klopper, W.; Jenneskens, L. W.; Lutz, M.; Spek, A. L.; v an Koten, G. Chem. Eur. J. 2004 10 1331 1344. 1 6 ) Singleton, J. T. Tetrahedron, 2003 59 1837 1857. 1 7 ) Ohff, M.; Ohff, A.; van der Boom, M. E.; Milstein, D. J. Am. Chem. Soc. 1997, 119 11687 11688.

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77 1 8 ) Morales Morales, D.; Grause, C.; Kasaoka, K. ; Redon, R.; Crammer, R. E.; Jensen, C. M. Inorg. Chem. Acta 2000, 300 302, 958 963 19 ) Ray, A.; Zhu, K.; Kissin, Y. V.; Cherian, A. E.; Coates, G. W.; Goldman, A. S. Chem. Commun. 2005 3388 3390. 2 0 ) Miyaura, N.; Yamada, K.; Suginome, H.; Suzuki, A. J. Am. Chem. Soc 1985 107 (4) 972 980. 2 1 ) Kharasch, M. S.; Engelmann, H.; Mayo, F. R. J. Org. Chem 1938 2 288. 2 2 ) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry ; Uni versity Science Books: Mill Valley, CA, 1987 2 3 ) Parshall, G. W.; Ittel, S. D. Homogenous Catalysis ; Wiley & Sons, Inc: New York, 1992 2 4 ) Crabtree, R. H. The Organometallic Chemistry of the Transition Metals 4th Ed, Wiley & Sons, Inc: Hoboken, 2005 2 5 ) Zucca, A.; Petretto, G. L.; Stoccoro, S.; Cinellu, M. A.; Minghetti, G.; Manassero, M.; Manassero, C.; Male, L.; Albinati, A. Organometallics 2006, 25, 3996 4001. 2 6 ) Zhang, Y.; Wang, J.; Mu, Y.; Shi, Z.; Lu, C.; Zhang, Y.; Qiao, L.; Feng, S. Or ganometallics 2003, 22, 4715 4720. 2 7 ) Fossey, J. S.; Richards, C. J. Organometallics 2002, 21, 5259 5264. 2 8 ) Morrison, D. L.; Rodgers, P. M.; Chao, Y.; Bruck, M. A.; Grittini, C.; Tajima, T. L; Alexander, S. J.; Rheingold, A. L.; Wigley, D. E. Organo metallics 1995, 14, 2435 2446. 29 ) Cummins, C. C.; Beachy, M. D.; Schrock, R. R.; Vale, M. G.; Sankaran, V.; Cohen, R. E. Chem. Mater. 1991 3 (6) 1153 1163. 3 0 ) Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. 2000 65 1144 1157. 3 1 ) Wolfe, J. P.; Waga w, S.; Buchwald, S. L. J. Am. Chem. Soc. 1996 118 7215 7216. 3 2 ) Daniele, S.; Hitchcock, P. B.; Lappert, M. F.; Nile, T. A.; Zdanski, C. M. J. Chem. Soc ., Dalton Trans 2002 3980 3984. 3 3 ) Chisholm, M. H.; Bradley, D. C. J. Chem Soc (A) 1971 2741 2 743. 3 4 ) Ruggli, P.; Prijs, B. Helvetica Chimica Acta 1945 28 674 690. 3 5 ) Jones, R. G.; Karmas, G.; Martin Jr, G. A.; Gilman, H. J. Am. Chem. Soc 1956 78 4285 4286.

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78 3 6 ) Bochmann, M.; Wilkinson, G.; Hussain, B.; Motevalli, M.; Hursthouse, M.B. P olyhedron 1988, 7 1363 1370. 3 7 ) Chisholm, M. H.; Hammond, C. E.; Huffman, J. C. Polyhedron 1989 8 129 131. 38 ) Chisholm, M. H.; Reichert, W. W.; Thornton, P. J. Am. Chem. Soc. 1978 100 (9) 2744 2748 39 ) Greco, G. E.; Schrock, R. R. Inorg. Chem. 2001, 40, 3850 3860. 4 0 ) Listemann, M. L.; Schrock, R. R.; Dewan, J. C.; Kolodziej, R. M. Inorg. Chem 1988, 27(2) 264 271. 4 1 ) Yasuda, H.; Nakayama, Y.; Takei, K.; Nakamura, A.; Kai, Y.; Kanehisa, N. J. Organometallic Chem 1994, 473, 105 116. 4 2 ) Zhang, Y.; Wang, J.; Mu, Y.; Shi, Z.; Lu, C.; Zhang, Y.; Qiao, L.; Feng, S. Organometallics, 2003 22, 3877 3883. 4 3 ) Du, C, J, F,; Hart, H.; Ng, K, K. D. J. Org. Chem 1986 51 3162 3165.

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79 BIOGRAPHICAL SKETCH Adam Rand Carlson was born in 1979 in Ceda r Rapids, Iowa. He graduated with a B.A. in chemistry from The University of Northern Iowa in 2003. After graduation Adam spent two years doing masters research in analytical chemistry at the University of Northern Iowa. He came to the University of Flo rida in 2005 and joined the Veige Group. Upon completion of his M.S. program, Ad am moved to San Antonio, Texas and is currently employed with D.R. Horton.


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