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Chemistry of Deca- and Dodeca-Closo-Borate Bearing Three Exopolyhedral Sulfur Substituents

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Chemistry of Deca- and Dodeca-Closo-Borate Bearing Three Exopolyhedral Sulfur Substituents CHEMISTRY OF DECA- AND DODECA-CLOSO-BORATE BEARING THREE EXOPOLYHEDRAL SULFUR SUBSTITUENTS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Hoitung Terry Leung ***** The Ohio State University 2004 Dissertation Committee: Approved by Professor Sheldon Shore, Advisor Professor Ross Dalbey _________________________________ Professor Claudia Turro Advisor Department of Chemistry ABSTRACT Chemistry of mercaptan-closo-decaborate was extended from mono-substituted isomers to a new tri-substituted species. The previously reported procedure of 2- synthesizing 1,10-(Me2S)2-2-MeS-B10H7 from [B10H10] was found irreproducible. The method was modified and the overall yield was improved. Even though the degree of substitution was found to be controlled by time and temperature, the increase of reaction time and temperature did not produce further (or tetrakis) substituted product. The tri- subsituted compound of closo-dodecaborate system, 1,7-(Me2S)2-9-MeS-B12H9, was synthesized from 1,7-B12H10(SMe2)2. Analogously halogenations of 1,10-B10H8(SMe2)2 and 1,7-B12H10(SMe2)2 produced compounds with a general formula of 2-X-1,10- (Me2S)2-B10H7 and 9-X-1,7-(Me2S)2-B12H9, respectively. The existence of cationic + + intermediates, [1,2,10-B10H7(Me2S)3] and [1,7,9-(Me2S)3-B12H9] , were examined and witnessed by 11B and 11B{1H} NMR. Dealkylation of these boron cages led to the corresponding tri-thioether as well as tri-thiol products. They were found reacted with methylene chloride. Due to the decrease of reactivity by gradual substitution of the boron cage, the reaction was not complete. Mono-substituted compounds were employed to demonstrate this unusual nucleophilicity of decaborane(10). ii 1- The isolation procedure of [2-B10H9SMe2] was previously reported with a small 1- contamination of [1-B10H9SMe2] . This was when they were synthesized from DMSO 2- and [B10H10] . We discovered that this isomer can be purified by dealkylating to [2- 2- B10H9SMe] and realkylating with methyl iodide. Both of the isomeric thioethers of 2- [B10H9SMe] demonstrated their nucleophilicities in the formation of 1- [B10H9SMe((CH2)nX)] by reacting with alkyl chloride and other halides. Subsequently, 2- the thioethers led to the production of the corresponding thiols, [1-B10H9SH] and [2- 2- B10H9SH] , with combined yield of over 60% isolated, significantly higher than other synthetic methods. All new compounds have been characterized by multinuclear NMR and either mass-spactrometry or elemental analysis. Some of their molecular structures have been obtained by single-crystal X-ray diffraction studies. iii DEDICATION To My Parents and family iv ACKNOWLEDGMENTS I would like to thank my advisor, Professor Sheldon G. Shore, for his support intellectually and financially in all these years. He has given me a lot of freedom in my research. He guided me to the right directions with his patience and experiences, not only on my work, but also on how to be a better person. I am very thankful to everyone who had helped me or been my companions in the Department of Chemistry here in The Ohio State University, especially the Shore group members. My friends and co-workers have taught me a great deal of chemistry as much as some valuable lessons in life. I would like to thank Dr. Roman Kultyshev especially for being a great friend as well as a mentor. I am grateful to Drs. Xuenian Chen, Biu Du, Shengming Liu, and Edward A. Meyers who did most of the work on the crystal structures contained herein, sometimes even sacrificing their own work. I would also like to thank my friends and coworkers Drs. Errun Ding and Christine Plečnik for their help and support. Special thanks go to Dr. Ewan Hamilton, Seth Kerechanin and Duane Wilson for proofreading this dissertation. I extend my gratitude to the Department of Chemistry of The Ohio State University for providing the opportunity to grow as a scientist. v VITA May 28th 1974. Born – Hong Kong May 1998. Bachelor of Science University of Hawaii at Manoa 1998 – 2002. .Teaching Asst. The Ohio State University. 2002 – 2004. Reasearch Asst. The Ohio State University. PUBLICATIONS Research Publications 1. Kultyshev, Roman G.; Liu, Shengming; Leung, Hoitung T.; Liu, Jianping; Shore, Sheldon G., “Synthesis of Mono- and Dihalogenated Derivatives of (Me2S)2B12H10 and Palladium-Catalyzed Boron-Carbon Cross-Coupling Reactions of the Iodides with Grignard Reagents.” Inorg. Chem., 42, 3199-3207, (2003). FIELDS OF STUDY Major Field: Chemistry vi TABLE OF CONTENTS P a g e Abstract . .ii Dedication . .iv Acknowledgments . .v Vita . .vi List of Tables . .x List of Figures . xii List of Schemes . xv Chapters: 1. Introduction 2- 2- 1.1 Structure and properties of [B10H10] and [B12H12] . .1 2- 2- 1.2 Synthesis of [B10H10] and [B12H12] . .2 1.3 Stereochemistry on the boron clusters substituents 1.3.1 Dodecaborane(12) . 5 1.3.2 Decaborane(10) . 6 1.4 Charge-compensated closo-borane compounds and reaction properties. 8 vii 2- 2- 1.5 Selectivity in reactions of [B10H10] and [B12H12] 1.5.1 Halogenation . .9 1.5.2 Diazonium derivatives . 11 1.5.3 Carbonyl derivatives . .11 1.5.4 Sulfonium derivatives . .13 1.5.5 Mercapto derivatives . .15 2. Result and Discussion A. Synthesis of Metal Linker and Potential Formation of Linkages A2.1 Synthesis of 1,10-B10H8(N2)2 and Reactions . 16 2- A2.2 Development in Synthesizing [1,10-B10H8(CN)2] A2.2.1 Through 1,10-B10H8(N2)2 . 20 A2.2.2 Through 1,10-B10H8(IPh)2 . .21 B. Chemistry of inner sulfonium derivatives of deca- and dodeca-closo-borate B2.1 1,10-(Me2S)2-2-MeSB10H7 . .36 + B2.2 First Cationic Trisubstituted Isomers [1,2,10-B10H7(SMe2)3] . 40 B2.3 Neutral Icosahedral closo-dodecaborane bearing 3 exopolyhedral sulfur substituents . 51 B2.4 Halogenation of 1,10-B10H8(SMe2)2, 1,10-B10H8(N2)2 and 1,7-B12H10(SMe2)2 . .62 2- B2.5 Dealkylation of 1,10-(Me2S)2-2-MeSB10H7 to [1,2,10-B10H7(SMe)3] . 66 B2.6 Reduction and oxidation of 1,10-(Me2S)2-2-MeSB10H7 . 73 1- B2.7 Isolation and characterization of 1- and 2-[B10H9SMe2] . .82 B2.8 Synthesis of methyl thioether and thiols from inner sulfonium salts . .90 viii B2.9 Reaction of methyl thioethers with electrophilic reagents . .101 B2.9.1 Reaction of [Me4N]2[2-B10H9SMe] with methyl iodide . 102 2- B2.9.2 Reaction of isomeric [B10H9SMe] with dihaloalkanes . .105 2- B2.9.3 Reaction of isomeric [B10H9SMe] with alkyl halides . .119 2- B2.9.4 Tertiary Alkylation of [1-B10H9SMe] by Michael Addition . .122 2- B2.9.5 Reaction of [1-B10H9SMe] with 1,1-Dichloroacetone . 124 2- B2.9.6 Reaction of [1(2)-B10H9SMe] with unsaturated alkyl halides . .129 3. Experimental 3.1 Apparatus . .136 3.2 Reagents . .138 2- A3 Synthesis of [1,10-B10H8(CN)2] . 140 B3.1 Reactions of 1,10-(Me2S)2-2-MeSB10H7 and 1,7-(Me2S)2-9-MeSB12H9 . 141 B3.2 Halogenation of boron cages . .148 1- B3.3 Synthesis of 1- and 2-[B10H9SMe2] and related reactions . .150 1- B3.3.1 Dealkylation of [2-B10H9SMe2] . 151 2- B3.3.2 Alkylation of [1(2)-B10H9SMe] . 154 List of References . .163 ix LIST OF TABLES Table Page 1 Crystal data and structure refinement for 1,10-B10H8(IC6H5)2 . .27 2 Selected Bond Distances of 1,10-B10H8(IC6H5)2. 29 3 Selected Bond Angles of 1,10-B10H8(IC6H5)2 . 30 4 Crystal data and structure refinement for [1,2,10-B10H7(SMe2)3]BF4 . 46 5 Selected Bond Distances of [1,2,10-B10H7(SMe2)3]BF4 . 47 6 Selected Bond Angles of [1,2,10-B10H7(SMe2)3]BF4 . .48 7 Crystal data and structure refinement for 1,7-(Me2S)2-9-MeSB12H9 . 57 8 Selected Bond Distances of 1,7-(Me2S)2-9-MeSB12H9 . 58 9 Selected Bond Angles of 1,7-(Me2S)2-9-MeSB12H9 . 59 10 Crystal data and structure refinement for 1,10-(Me2S)2-2-MeSO2-B10H7 . 77 11 Selected Bond Distances of 1,10-(Me2S)2-2-MeSO2-B10H7 . .79 12 Selected Bond Angles of 1,10-(Me2S)2-2-MeSO2-B10H7 . 80 13 Crystal data and structure refinement for [Bu4N][2-B10H9SMe2] . 88 14 Selected Bond Distances and Angles of [Bu4N][2-B10H9SMe2] . 89 15 Crystal data and structure refinement for [MePPh3]2[2-B10H9S] . 98 16 Selected Bond Distances and Angles of [MePPh3]2[2-B10H9S] . .100 x 17 Varied chemical shifts of alkylated products with different dihaloalkanes . 109 1- 18 Structure refinement for 1- and 2-[(MeSCH2Cl)-B10H9] . .113 1- 19 Selected Bond Distances of [1-(MeSCH2Cl)-B10H9] . .115 1- 20 Selected Bond Distances of [2-(MeSCH2Cl)-B10H9] . 116 1- 21 Selected Bond Angles of 1- and 2-[(MeSCH2Cl)-B10H9] . .117 22 Varied chemical shifts of alkylated products with different alkyl iodides . .120 23 Crystal data and refinement for Me4N [1-(MeSCH2CHCH2)-B10H9] . .132 24 Selected Bond Distances and Angles Me4N [1-(MeSCH2CHCH2)-B10H9] . .134 xi LIST OF FIGURES Figure Page 2- 2- 1 Convention of labeling closo-[B10H10] and closo-[B12H12] . 4 14 2 N NMR spectrum of 1,10-B10H8(N2)2 . .18 3 11B-11B COSY NMR spectrum of reaction solution between 1,10-B10H8(N2)2 / KCN . 22 4 Mass spectrum of products in 1,10-B10H8(N2)2 reaction with KCN . .23 11 5 B NMR spectrum of 1,10-B10H8(IC6H5)2 . 26 6 Crystal structure of 1,10-B10H8(IC6H5)2 . 28 7 Packing of 1,10-B10H8(IC6H5)2 in a single crystal .
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