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Ligand David Peter Klein Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 2004 Chemistry of ruthenium complexes incorporating the doubly-linked bis(dimethylsilylcyclopentadienyl) ligand David Peter Klein Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Klein, David Peter, "Chemistry of ruthenium complexes incorporating the doubly-linked bis(dimethylsilylcyclopentadienyl) ligand " (2004). Retrospective Theses and Dissertations. 1138. https://lib.dr.iastate.edu/rtd/1138 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Chemistry of ruthenium complexes incorporating the doubly-linked bis(dimethylsilylcyclopentadienyl) llgand by David Peter Klein A thesis submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Inorganic Chemistry Program of Study Committee: Robert J. Angel ici, Major Professor Victor Lin Gordon J. Miller Marc Porter Mark S. Gordon Iowa State University Ames, Iowa 2004 UMI Number: 3145699 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. UMI UMI Microform 3145699 Copyright 2004 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 ii Graduate College Iowa State University This is to certify that the doctoral dissertation of David Peter Klein has met the dissertation requirements of Iowa State University Signature was redacted for privacy. Major Profess Signature was redacted for privacy. For me Major Program iii For the people who mean the most to me, My Wife, Erin My Mother and Father, Jacob and Linda My Siblings, Michael, Mark, And Jessica iv TABLE OF CONTENTS ABSTRACT ix CHAPTER 1. GENERAL INTRODUCTION 1 Thesis Organization 1 Literature Review 1 Schemes Scheme 1 7 Scheme 2 8 Scheme 3 9 Tables Tabic 1. Late transition metals that catalyze hydroamination of 6-aminohex-1 -yne (Eq 7) 10 References 11 CHAPTER 2. A NEW MECHANISM FOR THE INTERMOLECULAR HYDROAMINATION OF ALKYNES: CATALYSIS BY DINUCLEAR RUTHENIUM COMPLEXES WITH A RIGID DI-CYCLOPENTADIENYL LIGAND 13 Abstract 13 Introduction 14 Results and Discussion 15 Intermolecular Hydroamination Catalyzed by Complexes 1,2, 3a/3b, and 8 15 Proposed Mechanism for the Hydroamination of Alkynes as Catalyzed by Complexes 1,2,3a/3b, and 8 18 Conclusion 27 Experimental Section 28 General Considerations 28 Synthesis of {(!?"-C5H3)2(SiMe2)2}Ru2(CO)20!rCO){//2-^\77^C(Ph)=C(H)} (2) 29 Synthesis of {(^-CsHsMSiMezMRuzfCO^-PhCz^+BF^ (3a/3b) 30 Synthesis of {(i?^-C;H3)2(SiMe2)2}Ru2(CO)3 7/-C(H)=C(H)Ph}+BF4" (7) 31 Synthesis of {(9?^C$H3)2(SiMe2)2}Ru2(CO)3[NH2(p-MeC6H4)]H^BF4- (8) 32 General Procedure for the Catalytic Hydroamination Reaction 32 Synthesis of (p-FC6H4)MeC=N(p-MeC6H4) 33 Molecular Structure Determinations of (2) and (7) 34 Acknowledgement 35 Tables Table 1. Hydroamination of Acetylenes Catalyzed by (1), (3a/3b), and (8) 36 Table 2. Crystal data and structure refinement for (2) and (7) 37 Schemes Scheme 1 38 Scheme 2 39 Figures Figure 1 40 Figure 2 41 References 42 CHAPTER 3. SQUARE PLANAR AND BUTTERFLY TETRANUCLEAR RUTHENIUM CLUSTERS INCORPORATING THE DOUBLY-LINKED BIS(DIMETHYLSILYLCYCLOPENTADIENYL) LIGAND 44 vi Introduction 44 Results and Discussion 45 Synthesis of {(^-CAMSiMezMR^CO)^ (2) 45 Reaction of {(T^-QHsMSiMei):} Rti2(CO)4 (1) with dihydrogen 46 Proposed mechanism for the formation of clusters 3 and 4 49 Photochemical details of the proposed mechanism 51 Conclusions 54 Experimental Section 54 General Considerations 54 Synthesis of (CpSiMez^RuzfCO^H? (2) 55 Reaction of (1) with Hydrogen 56 Synthesis of {(^-CsHaMSiMezMzRu^CO^EL, (3) and {(%S-C5H3MSiMe2)2}2Ru4(CO)4H4(4) 57 Crystallographic Structural Determinations of (3) and (4) 57 Acknowledgement 58 Tables Table 1. Crystal data and structure refinement for (3) and (4) 59 Schemes Scheme 1 60 Scheme 2 61 Scheme 3 62 Scheme 4 63 Figures vii Figure 1 64 Figure 2 65 Figure 3 66 References 67 CHAPTER 4. THERMODYNAMIC AND KINETIC ACIDITY OF DINUCLEAR RUTHENIUM COMPLEXES CONTAINING A RIGID DICYCLOPENTADIENYL LIGAND 70 Introduction 70 Results and Discussion 71 Synthesis and protonation of {(^"C^MSiMei);}Ruz(CO)] {P(OR)a}, R= Me(2),Ph(3) 71 Thermodynamic Acidity of [{(ifCsH3MSiMe2)2}Rii2(CO)3{P(OR)3}H]+BF4- {R = Me (2H^BF4'), Ph (3HIBF4 )} 74 Kinetic Acidities of [{(,f CAMSiMezMRt^CO^ {PfORMH]^' {R = Me (2H+BF4-), Ph (3ITBF4')} 74 Conclusions 78 Experimental Section 79 General Considerations 79 Synthesis of {(^#3)2^62)2^112(00)3{^(OMe))} (2) 80 Synthesis of {(ifCsHsMSiMezMRi^CO^{P(OPh)3} (3) 81 Synthesis of {(^'CsHaMSiMezMRuzfCOb{P(OMe)3}H^BF4 (2H+BF4 ) 82 Synthesis of {(i?^'C5H3)2(SiMe2)2}Rii2(CO)3{P(OPh)3}H^BF4" (3H+BF4 ) 82 Kinetic studies of the reaction of 2H+BF4_ and 3H+BF4_ with amine bases 83 + + - Thermodynamic Acidity Measurements of 2H BF4" and 3H BF4 84 Schemes viii Scheme 1 86 Scheme 2 87 Scheme 3 88 Figures Figure 1 89 Figure 2 90 Tables Table 1. Pseudo-first-order rate constants for the reaction of amines and complex 2H+BF4- according to Eq 4 in QHsNO? at 25.0 ± 0.1°C. 91 Table 2. Pseudo-first-order rate constants for the reaction of amines and complex 3H+BF4- according to Eq 4 in CgHgNOz at 25.0 ± O.V'C. 92 Table 3. First and Second-order rate constants for the reactions of 2H+BF4- and 3H^BF/ with amines according to Scheme 3 in CgH^NOz at25.0±0.1°C. 93 References 94 CHAPTERS. GENERAL CONCLUSIONS 96 ACKNOWLEDGMENTS 97 ix ABSTRACT This dissertation describes three investigations of the dinuclear ruthenium complex, 5 {(7? -C5H3)2(SiMe2)2}Ru2(CO)4: (1) its use as a catalyst for the hydroamination of alkynes by a new mechanism, (2) its reactions with % to give new ruthenium clusters containing bridging hydride ligands, and (3) the determination of thermodynamic and kinetic acidities of 5 + two related complexes, {(77 -C5H3)2(SiMe2)2}Ru2(CO)3{P(OR) 3}H BF4" (R= Me, Ph). A fundamentally new mechanism for alkyne hydroamination catalyzed by the 5 + ruthenium complex, {0? -C5H3)2(SiMe2)2}Ru 2(CO)3(C2H4)H BF4", has been proposed. Many of the intermediates in the catalytic cycle have been isolated and/or characterized spectroscopically and found to react according to the proposed mechanism. The catalyst activity is terminated as a result of the isomerization of a bridging alkyne ligand in a key intermediate in the catalytic cycle. The butterfly cluster, {(ï^-C^MSiMezb}zRmfCO^K; , and the square planar 5 cluster, {(7? -C5H3)2(SiMe2)2}2Ru4(CO)4H4 , have been isolated from the photochemical 5 reaction of II2 with the doubly-linked dicyclopentadienyl complex, {(r/ - C5H3)2(SiMe2)2}Ru2(CO)4, in benzene. Wavelength-dependent photolysis studies suggest that the first step in the reaction of {(?^-CsH3)2(SiMe2)2}Ru2(CO)4 with H2 involves metal- metal bond cleavage. The reaction of the protonated phosphite complexes, {(i?5- C;H3)2(SiMe2)2}Rii2(CO)3{P(OR)3}H+BF4' (R= Me, Ph), with tertiary amines (DABCO, 4- methylmorpholine, NEt3, N(»-Bu)3) results in clean deprotonation of the metal-metal bond by the amine. Equilibrium measurements show that the P(OPh)3 complex is more acidic than the P(OMe)3 complex. The rates of deprotonation of the phosphite complexes have been X determined, and follow the rate law: Rate = [complex] + ^[amine][complex]. Comparisons of the ki rate constants reveal that the reactions are much more sensitive to the steric properties of the amine and metal complex than to electronic factors. 1 CHAPTER 1. GENERAL INTRODUCTION Thesis Organization The body of work presented in this thesis is a summary of my accomplishments at Iowa State University, and includes discussions of the synthesis, characterization, and mechanistic and kinetic studies of reactions of a variety of diruthenium organometallic complexes. The first chapter contains a brief background describing previously-proposed mechanisms of catalytic hydroamination, and the subsequent chapter describes studies that led to a new mechanism for this process. Successive chapters describe extensions of the chemistry of other diruthenium complexes to reactions with hydrogen and the acidity of diruthenium complexes with bridging hydride ligands. Each chapter is independent, and any equations, figures, schemes, tables or references pertain to that chapter only. Literature Review Reactions of carbon-carbon multiple bonds (alkenes or alkynes) with various substrates (Hz, amines, halogens, water, alcohols, etc) are fundamental to the synthesis of organic compounds. Although the addition of the more common reagents (hydrogen, halogens, water and alcohols) to alkenes and alkynes can be considered routine, the addition of amines, i.e hydroamination (Eq 1), is much more difficult.1 There is much interest in the (1) products of these reactions (enamines, imines, amines, and ketones) as reagents in the synthesis of more complex organic frameworks.
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