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(PCP)Ir COMPLEXES with SMALL MOLECULES REACTIONS OF (PCP)Ir COMPLEXES WITH SMALL MOLECULES by SABUJ KUMAR KUNDU A Dissertation submitted to the Graduate School-New Brunswick Rutgers, The State University of New Jersey in partial fulfillment of the requirements for the degree of Doctor of Philosophy Graduate Program in Chemistry written under the direction of Professor Alan S. Goldman and approved by ________________________ ________________________ ________________________ ________________________ New Brunswick, New Jersey January, 2010 ABSTRACT OF THE DISSERTATION REACTIONS OF (PCP)Ir COMPLEXES WITH SMALL MOLECULES By SABUJ KUMAR KUNDU Dissertation Director: Professor Alan S. Goldman R4 3 Iridium pincer complexes ( PCP)IrH n (PCP=[ κ -2,6-C6H3(CH 2PR 2)]) are effective catalysts for the dehydrogenation of alkanes. We wished to design pincer ligands in which the set of phosphinoalkyl groups would offer (a) maximal steric "protection" against cluster-formation (b) minimal hindrance to C-H addition, and (c) resistance to decomposition and self-dehydrogenation (unlike iPr groups). Thus, we have tBu3Me t t synthesized iridium complexes of ligands PCP ([C 6H3(CH 2P BuMe)(CH 2P Bu 2]). tBu3Me ( PCP)IrH 4 (1) shows more efficiency in dehydrogenation of alkanes than either tBu4 iPr4 tBu3Me ( PCP)IrH n or ( MePCP)IrH n. ( PCP)IrH 4 was also found to be a very effective catalyst in alkane metathesis. Although isocyanides are important building blocks in organic synthesis, their commercial availability is limited compared to other chemicals. (PCP)Ir complexes react with different secondary methyl amines and at ambient temperature to form corresponding iridium isocyanide complexes (PCP)Ir(H)(H)(CNR), 3-1 (a-e) which react with CO forming (PCP)Ir(CO) to liberate the corresponding isocyanide. ii The addition of PhCCH to highly stable complexes, (PCP)IrL (L = CO, CNR), is challenging. (PCP)IrL (L = CO, CNR) complexes react with PhCCH in presence of acid to form complex (PCP)Ir(CO)(H)(CCPh) ( 5-3) and (PCP)Ir(CNBz)(H)(CCPh) ( 5-1) , respectively, in which hydride and acetylide group are trans to each other. The reaction proceeds via the cationic intermediate [(PCP)Ir(CO)(H)] +. Solid-supported catalysts have significant advantages over homogeneous systems, particularly with respect to product-catalyst separation. We have investigated several routes to the development of supported pincer-ligated iridium catalysts. The p- dimethylamino-substituted PCP complex is found to bind strongly to alumina while maintaining the same high activity (or even slightly greater) for alkane-dehydrogenation as found in the solution phase. A broad range of (PCP)Ir complexes with widely varying steric and electronic effects have been synthesized and studied including (PCP)IrL, (PCP)Ir(H)(H)L and PCP)Ir(H)(Cl)L, (L = various P- and N-donors, N 2, various olefins). The relative thermodynamics of these adducts have been detected by equilibrium measurements and calculated using DFT. 3 Precursors of “(PCP)Ir” cleaves sp C −O bonds of various esters (RCO 2R1, R 1= alkyl) to give (PCP)Ir(R 1)(O 2CR) or, in cases where R 1 has a β-hydrogen, (PCP)Ir(H)(O 2CR) plus the corresponding alkene derived from R 1. iii Dedication To my family and village iv Acknowledgement I would like to thank my advisor, Prof. Alan S. Goldman for being the best possible boss whom I could have asked for. His perpetual energy and enthusiasm in research, continuous support, staying cool even knowing I am taking stupid, helpful advice all the time, not only greatly motivate me but also taught me the importance of fundamentally understanding the chemistry. I will never forget the freedom he provided me for exploring different projects. I would like to specially thank my committee members, Prof. Karsten Krogh- Jespersen, Prof. Ralf Warmuth and Prof. Benjamin J. Glasser, who served on my proposal committee, for their valuable time and helpful suggestions. I would like to thank Prof. Krogh-Jespersen and Yuriy Choliy for theoretical calculations, Dr. Tom Emge for the crystallographic analysis, and Dr. Seho Kim and Dr. Nagarajan Murali for their assistance with the NMR technique. I also thank Prof. Gene S. Hall for X-ray fluorescence measurements. I thank Prof. Maurice Brookhart and Zheng Huang at University of North Carolina at Chapel Hill for collaboration. I thank Dr. Elizabeth Pelczar and Dr. Amlan Ray, Dr. Yury Kissin for helping and teaching many techniques in the lab. I am thankful to my former and current lab members Dr. Long van Dinh, Zhuo Gao, Dr. Ritu Ahuja, Dr. Benudhar Punji, Dr. Sahar Elkhalafy, Dr. Agnieszka Nawara-Hultzsch, David Wang, Soumik Biswas, Kathleen Field, David Laviska, Jason Hackenberg, Dr. Rob Stibrany, Dr. Carolyn Supplee, and Dr. Burke Scott Williams; it was a great pleasure to work with them. v I am thankful to all of my friends here at Rutgers and in India who helped me to keep up my smile in the last five years. I feel a special gratitude toward my parents and sister Tanaya. Without their support and encouragement, it would be impossible for me from a rural village of India to reach what I am today. I thank Niloy, Antara and Kheya and Tutai, the new generations in our big family, my uncles and relatives in India. I also thank Bidisa, for her unconditional love and support. vi Table of Contents Abstract ii Dedication iv Acknowledgement v Table of Contents vii List of Tables xv List of Illustration xxi Chapter 1 Introduction 1 References 9 Chapter 2 Rational design and synthesis of highly active pincer-iridium 11 catalysts 2.1 Introduction 12 2.2 Results and Discussion 17 2.2.1 Computational Studies 17 R4 2.2.2 Synthesis of various ( PCP)IrH n complexes 20 tBu4 2.2.2.1 Synthesis of ( PCP)IrH 4 20 iPr4 2.2.2.2 Synthesis of ( PCP)IrH 4 20 tBu3Me 2.2.2.3 Synthesis of ( PCP)IrH 4 20 2.2.2.3.1 Synthesis of tBuMePH 20 2.2.2.3.2 Synthesis of monophosphine ligand 21 vii salt 2.2.2.3.3 Synthesis of ligand salt ( 4) and 21 ligand ( 5) tBu3Me 2.2.2.3.4 Synthesis of ( PCP)IrHCl (6) 22 tBu3Me and ( PCP)IrH 4 (1) 2.2.3 Transfer dehydrogenation study of alkane using different 22 PCP-pincer catalysts 2.2.3.1 Transfer dehydrogenation of n-octane using 23 different pincer catalysts 2.2.3.2 Transfer dehydrogenation of 4-propylheptane 30 2.2.3.3 Resting state of the catalyst during transfer 32 dehydrogenation 2.2.3.4 Transfer dehydrogenation of cyclooctane using 33 NBE and 1-hexene acceptor 2.2.4 Acceptorless dehydrogenation using different pincer 35 catalysts 2.2.4.1 Acceptorless dehydrogenation of cyclodecane 36 using different pincer catalysts 2.2.4.2 Acceptorless dehydrogenation of n-undecane 38 2.2.5 Competition transfer dehydrogenation experiments: n- 40 octane vs. COA 2.2.6 Alkane metathesis 41 2.2.6.1 Alkane metathesis of n-hexane using pincer 41 viii iridium and Schrock’s catalyst 2.2.6.2 Alkane metathesis of cyclooctane using pincer 42 iridium and Schrock’s catalyst 2.3 Conclusions 44 2.4 Experimental 46 2.5 References 55 Chapter 3 Synthesis of isocyanides from secondary methyl amine 63 using (PCP)Ir 3.1 Introduction 64 3.2 Results and discussion 65 3.2.1 Reaction of (PCP)Ir with N -methylphenylamine 65 3.2.2 Reaction of (PCP)Ir with N -methylcyclohexylamine, N- 66 methylbutylamine and N-methylethylamine 3.2.3 Reaction of (PCP)Ir with N-methylbenzylamine 67 3.2.4 Mechanistic investigation 69 3.2.5 To test if formation of isocyanide is catalytic 71 3.2.5.1 N-methylbenzylamine and (PCP)Ir 71 3.2.5.2 N-methylphenylamine and (PCP)Ir 71 3.3 Experimental 72 3.4 References 80 Chapter 4 Oxidation addition of MeI to (PCP)Ir carbonyl and isocyanide 84 complexes ix 4.1 Introduction 85 4.2 Results and Discussion 85 4.2.1 Reaction of (PCP)Ir(CO) with MeI 85 4.2.1 Reaction of (PCP)Ir(CNBz) with MeI 86 4.3 Experimental 88 4.4 References 90 Chapter 5 Acid catalyzed addition of phenyl acetylene to (PCP)Ir(CO) 97 and (PCP)Ir(CNBz) 5.1 Introduction 98 5.2 Results and Discussion 98 5.2.1 Synthesis and characterization of 98 (PCP)Ir(CNBz)(H)(CCPh) (H and CCPh trans ) ( 5-1) 5.2.2 Synthesis and characterization of 99 (PCP)Ir(CNBz)(H)(CCPh) (H and CCPh cis ) ( 5-2) 5.2.3 Synthesis and characterization of (PCP)Ir(CO)(H)(CCPh) 100 (H and CCPh trans ) ( 5-3) 5.2.4 Synthesis and characterization of (PCP)Ir(CO)(H)(CCPh) 101 (H and CCPh cis ) ( 5-4) 5.2.5 Reaction of (PCP)Ir(CO) with CH 3NO 2 101 5.2.6 Reaction of (PCP)Ir(CNBz) with CH 3NO 2 102 5.2.7 Reaction of (PCP)Ir(CO) with PhOH 102 5.2.8 Reaction of (PCP)Ir(CO) with a (1:1) mixture of PhCCH 103 and PhOH x 5.2.9 Mechanistic investigation 105 5.2.10 Proposed structure of UN1, UN2 and UN4 108 5.3 Experimental 109 5.4 Conclusions 114 5.5 References 115 Chapter 6 Synthesis and catalytic activity of heterogenized (supported) 128 pincer-ligated iridium catalysts for alkane dehydrogenation 6.1 Introduction 129 6.2 Results and discussion 129 6.2.1 Different strategies toward making supported pincer 129 catalysts 6.2.2 Covalent attachment of iridium pincer complexes to silica 129 6.2.2.1 Removing CO from (PCP)Ir(H)(I)(CO) 132 6.2.3 Alumina-supported iridium pincer catalyst systems 133 6.2.3.1 Transfer-dehydrogenation of COA by solution- 134 phase and γ-alumina-supported catalyst systems 6.2.3.2 n-octane transfer-dehydrogenation by (Me 2N- 137 PCP)IrH 2 6.2.3.3 γ-Alumina (no Ir) isomerizes 1-octene 138 6.2.3.4 Infrared spectroscopic characterization of the 140 PCP complexes supported on γ-alumina Quantifying the strength of binding of the xi Me 2N-PCP unit to alumina 6.2.3.5 Quantifying the strength of binding of the 141 Me 2N-PCP unit to alumina 6.3 Conclusion 142 6.4 Experimental 143 6.5 References
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