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Download File A Journey Across the Periodic Table: The Synthesis and Characterization of Main Group Metals Supported by Nitrogen– or Sulfur–Rich Ligands Neena Tiscza Chakrabarti Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate School of Arts and Sciences Columbia University 2014 © 2014 Neena Tiscza Chakrabarti All Rights Reserved A Journey Across the Periodic Table: The Synthesis and Characterization of Main Group Metals Supported by Nitrogen– or Sulfur–Rich Ligands Neena Tiscza Chakrabarti Abstract In Chapter 1, I discuss the synthesis and characterization of lithium tris(pyrazolyl)hydroborato complexes, [TpR1,R2]Li. Group 1 [TpR1,R2]M complexes serve as key starting points to access many other main group and transition metal complexes; however, the synthesis and crystal structures of [Tp R1,R2]Li has not been reported. t t Molecular structures of [TpBu ]Li and [TpBu ,Me]Li show these complexes are trigonal pyramidal, an unusual geometry for lithium. These complexes are also able to bind small molecules to form four-coordinate pseudo-tetrahedral complexes, [Tp]Li-L (L = But MeCN, pz H, and H2O). The binding constants for the association of acetonitrile to t t [TpBu ]Li and [TpBu ,Me]Li are 0.84M-1 and 0.96M-1, respectively, indicating that the t dissociation of MeCN is facile in solution. In addition, [TpBu ,Me]Li serves as t transmetallating agent to yield the cadmium halide complexes, [TpBu ,Me]CdX (X = Cl, Br, I). In Chapter 2, I discuss the synthesis and characterization of organometallic cadmium complexes supported by the nitrogen-rich multidentate ligands, tris(pyridylthio)methane, [Tptm]H; tris(1-methyl-imidazolylthio)methane, [TitmMe]H; and tris(1-methyl-benzimidazolylthio)methane, [TitmiPrBenz]H. These ligands are in the nascent stages of development and there are only a few metal [Tptm] and [TitmMe] complexes in the literature. An investigation of the reactivity of [L]CdN(SiMe3)2, Me iPrBenz [L]CdOSiMe3, and [L]CdOSiPh3 ([L] = [Tptm], [Titm ], [Titm ]) shows these complexes provide access to a variety of organometallic cadmium complexes, [L]CdX, (X = OAc, Cl, Br, O2CH, NCO). The characterization of cadmium acetate and formate complexes is significant due to their structural similarity with the metal bicarbonate intermediate formed by zinc and cadmium-substituted carbonic anhydrase. In addition, the synthesis and characterization of cadmium methyl complexes, [L]CdMe, is iPrBenz discussed. The application of heat to a mixture of [Titm ]H and CdMe2 results in iPrBenz iPrBenz isomerization of the ligand to [S3-Titm ]CdMe. This sulfur-rich [S3-Titm ] ligand is not reported in the literature and is ripe for further investigation. The solid state structures of these compounds provide a comparison with biologically relevant [Tp] or [Tm] cadmium methyl complexes in the literature. In Chapter 3, I describe the synthesis and structural characterization of ButBenz RBenz t [Bm ]M (M = Na, K) and [Bm ]Ca(THF)2 (R = Me, Bu ) are discussed. The sulfur- rich tripodal ligand tris(imidazolylthio)hydroborato, [Tm], was previously designed to serve as a softer version of the [Tp] ligand. Metal [Tm] complexes are prevalent in the literature and have often been used as molecular mimics of sulfur-rich enzyme active sites. Recently, the benzannulated [TmRBenz]M complexes were reported and were found to promote 3 coordination toward the metal center. To allow for an in-depth t investigation of the newly synthesized [BmRBenz] class of ligand, the [BmBu Benz]M (M = Na, K, Ca) complexes were synthesized and compared to previously reported metal MeBenz BmMeBenz [Bm ]M complexes. Additionally, the [ ]2Ca(THF)2 was synthesized and MeBenz characterized via X-ray diffraction. The molecular structure of [Bm ]2Ca(THF)2 shows the complex is monometallic with an uncommon eight-coordinate dodecahedral MeBenz calcium center. [Bm ]2Ca(THF)2 is the first molecular structure of calcium coordinated to the [Tm] or [Bm] ligand class. In Chapter 4, I discuss the synthesis and characterization of mercury alkyl complexes supported by the [TmMe], [BmR], [TmRBenz] and [BmRBenz] ligands (R = Me or But). As previously mentioned, [Tm]M complexes are considered biologically relevant t molecular models of enzyme active sites. With this in mind, [TmBu ]HgR (R = Me,Et) complexes have served as mimics for the mercury detoxification enzyme MerB. A previous study by our group showed that the adoption of multiple coordination modes t of the ligand in [TmBu ]HgR plays a significant role in the activation of the Hg-C bond toward protonolysis. The molecular structures of the [TmR], [BmR], [TmRBenz], and [BmRBenz] mercury alkyl complexes show that they adopt various coordination modes, ranging from 1 to 3. Preliminary competition experiments in which benzenethiol was added to [TmR]HgEt and [TmRBenz]HgEt indicate that the Hg-C bond in [TmMeBenz]HgEt t was cleaved faster than that in [TmMe]HgEt. Conversely, the Hg-C bond in [TmBu ]HgEt t was cleaved faster than that in [TmBu Benz]HgEt, indicating that benzannulation and the size of the R-group on the [Tm] ligand play important roles in Hg-C bond cleavage. TABLE OF CONTENTS List of Schemes, Figures, and Tables v Acknowledgements xviii Chapter 1. Synthesis and Structural Characterization of Uncommon Trigonal 1 Pyramidal Lithium Tris(pyrazolyl)hydroboration Complexes, Their Coordination to Small Molecules, and a Study of Their Reactivity 1.1 Introduction 4 1.1.1 Objective 4 1.1.2 The tris(pyrazolyl)hydroborato, [Tp], ligand 5 t t 1.2 Synthesis of [TpBu ]Li and [TpBu ,Me]Li Complexes 6 t t 1.3 [TpBu ]Li-L and [TpBu ,Me]Li-L Complexes 16 But But,Me 1.3.1 Synthesis and Molecular Structures of [Tp ]Li-L and [Tp ]Li-L 16 Complexes t t 1.3.2 DFT Calculations of [TpBu ]Li-L and [TpBu ,Me]Li-L 29 1.3.3 Equilibrium Studies of [Tp]Li and [Tp]Li-L Complexes 32 1.4 Reactivity of [TpR,R]Li complexes with Cadmium Halides Salts 43 1.5 Conclusion 52 1.6 Experimental Section 53 1.7 Crystallographic Data 67 1.8 Reference and Notes 73 i Chapter 2. Synthesis and Structural Characterization of Cadmium Complexes 80 Supported by Nitrogen-Rich Ligands: [Tptm], [TitmMe], and [TitmiPrBenz] and A Study of Their Reactivity 2.1 Introduction 83 2.1.1. Objective 83 2.1.2 The Ligand Systems 84 2.2 Synthesis of [Tptm]CdX Compounds 86 2.3 Synthesis of [TitmMe]CdX Compounds 95 i 2.4 Synthesis of [TitmPr Benz]CdX Complexes 102 2.5 Discussion of [L]CdN(SiMe3)2 Complexes 105 2.6 Discussion of [L]CdOSiR3 (R = Me, Ph) Complexes 110 2.7 Discussion of [L]CdMe 121 2.8 Discussion of [L]CdNCO 131 2.9 Discussion of [L]CdO2CX (X = H, Me) Complexes 139 2.10 Discussion of [L]CdX (X – Cl, Br, I) Complexes 147 2.11 Conclusion 155 2.12 Experimental Section 156 2.13 Crystallographic Data 187 2.14 References and Notes 197 Chapter 3. Synthesis and Structural Characterization of Bis(2-mercapto-1- 210 ii benzimidazolyl)hydroborato, [BmRBenz] (R = Me, But), Compounds of Sodium, Potassium and Calcium 3.1 Introduction 221 3.1.1 Objective 221 3.1.2 The tris(mercaptoimidazolyl)hydroborato, [Tm] and 222 bis(mercaptoimidazolyl)hydroborato, [Bm] class of ligands t 3.2 [BmBu Benz]M (M = Na, K) Compounds 224 RBenz t 3.3 Synthesis and Molecular Structure of [Bm ]2Ca(THF)2 (R = Me, Bu ) 227 MeBenz 3.4 [Bm ]2Ca(THF)2 as a l Agent 244 3.5 Conclusion 245 3.6 Experimental Section 245 3.7 Crystallographic Data 256 3.8 References and Notes 257 Chapter 4. Synthesis and Structural Characterization of Mercury Methyl and 253 Ethyl Complexes Supported by Sulfur-Rich [Tm] and [Bm] Ligands 4.1 Introduction 256 4.1.1 Objective 256 4.1.2 Rationalization for the [Tm] ligand 257 4.2 [Tm]HgR (R – Me, Et) complexes 260 4.2.1 Synthesis and Molecular Structures of [TmMe]HgR 260 iii MeBenz 4.2.2 Synthesis and Molecular Structures of [Tm ]HgR and 269 t [TmBu Benz]HgR 4.3 [Bm]HgR (R = Me, Et) Complexes 277 Me But 4.3.1 Synthesis and Molecular Structures of [Bm ]HgR and [Bm ]HgEt 277 MeBenz 4.3.2 Synthesis and Molecular Structures of [Bm ]HgR and 286 t [BmBu Benz]HgR 4.4 NMR Characterization of Mercury Alkyl Complexes 288 4.4.1 NMR Characterization of [L]HgMe Complexes 288 4.4.2 NMR Characterization of [L]HgEt Complexes 293 4.5 Hg-C Bond Cleavage with Benzenethiol 296 Me MeBenz 4.5.1 Reactions with [Tm ]HgEt and [Tm ]HgEt 296 t t 4.5.2 Reactions with [TmBu ]HgEt and [TmBu Benz]HgR 297 4.6 Conclusion 298 4.7 Experimental Section 298 4.8 Crystallographic Data 322 4.9 References and Notes 327 iv LIST OF SCHEMES, FIGURES AND TABLES Chapter 1 t t Scheme 1. Synthesis of [TpBu ]Li and [TpBu ,Me]Li 7 But 16 Scheme 2. Addition of small molecules (L = MeCN, Pz H, and H2O) to t t [TpBu ]Li and [TpBu ,Me]Li to obtain the [Tp]Li-L adduct t Scheme 3. Synthesis of [TpBu ,Me]CdX (X = Cl, Br, I) 45 Figure 1. Structure of a metal tris(pyrazolyl)hydroborato complex, 4 [TpR3,R5]M Figure 2. The cone angle () measured for [Tp]Co complexes 6 t Figure 3. Molecular Structure of [TpBu ]Li 8 t Figure 4. Molecular Structure of [TpBu ,Me]Li 8 Figure 5. Trigonal pyramidal coordination geometry 8 Figure 6. Variable temperature 1H NMR spectrum of the H-B bond in 12 But,Me [Tp ]Li in d8-toluene.
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