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Xerox University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 40106 I I I I 76-3531 REMMEL, Randall James, 1949- PREPARATION AND NUCLEAR MAGNETIC RESONANCE STUDIES OF THE ANIONS DERIVED FROM THE DEPROTONATION OF HEXABORANE(IO) DERIVATIVES; NMR STUDIES OF THE ANIONS DERIVED FROM THE POLYHEDRAL EXPANSION OF BORON HYDRIDE ANIONS BY DIB0RANE(6). The Ohio State University, Ph.D., 1975 Chemistry, inorganic X©rOX UniVOrSlty Microfilms, Ann Arbor, Michigan 48106 0 1975 RANDALL JAMES REMMEL ALL RIGHTS RESERVED THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED PREPARATION AND NUCLEAR MAGNETIC RESONANCE STUDIES OF THE ANIONS DERIVED FROM THE DE PROTONATION OF HEXABORANE(IO) DERIVATIVES; NMR STUDIES OF THE ANIONS DERIVED FROM THE POLYHEDRAL EXPANSION OF BORON HYDRIDE ANIONS BY DIBORANE(G) DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Randall J. Remmel, B.S. ***** Tne Ohio State University 1975 Reading Committee; Approved By Dr. Daniel L. Leussing Dr. Gary G. Christoph Dr. Sheldon G. Shore A (Aviser Department of Chemistry DEDICATION To Staci ii ACKNOWLEDGMENTS I sincerely thank Professor Sheldon Shore for his suggestions, support and encouragement during my tenure as a graduate student. I also thank my colleagues for their suggestions and discussions during the investigation. I also acknowledge financial support of this work by the National Science Foundation. ill VITA August 23, 1949 ............................Born - Peoria, Illinois 1 9 7 1 ....................................................B.S., Illinois State University 1971-1973 ................ ......................Teaching Associate, Department of Chemistry, The Ohio State University, Columbus, Ohio 1973-1975 ........................................Research Associate, Department of Chemistry, The Ohio State University, Columbus, Ohio PUBLICATIONS W.R. Clayton, A.V. Fratini, R.J. Remmel, and S.G. Shore, "2,6- Lutidine-Chloroborane, CyHgN- BH 2 CI, " Crystal Structure Communica tions , 3, 151 (1974). R.J. Remmel and S.G. Shore, "Nuclear Magnetic Resonance Studies of 2 -CH 3 B5 H0 " and 2 -BrBgH0 ~, " Abstracts of Papers, 168th Meeting, American Chemical Society, Atlantic City, 1974, p. INOR 059. R.J. Remmel, H.D. Johnson, II, l.S. Jaworiwsky, and S.G. Shore, "Pre paration and NMR Studies of the Stereochemically Nonrigid Anions: ^4^9~' ®5^12~' ®6^11~ ^ 7 ^ 1 2 ”' Syntheses of BgHii and BgHi2 ." J. Amer. Chem. Soc., in press (1975). FIELDS OF STUDY Major Field: Inorganic Chemistry Studies in Nonmetal Chemistry. Professors Sheldon G. Shore and Eugene P. Schram Studies in Transition Metal Chemistry. Professors Daryle H. Busch, Andrew A. Wojcicki, and Devon W. Meek iv TABLE OF CONTENTS Page DEDICATION........................................................................................................... 11 ACKNOWLEDGMENTS........................................................................................ Ill VITA ............................................................................................................................ Iv LIST OF TA BLES................................................................... vll LIST OF FIGURES ................................................................................................ vill INTRODUCTION.................................................................................................... I I Background of Hexaborane(lO) C h e m is tr y .............................. 1 II Brjz^nsted Acidity of the Boron H ydrides ..................................... 27 III Polyhedral Expansion of Boron Hydride A n io n s...................... 33 IV The Existence of a Heptaborane Species ................................. 39 V Background of Hexaborane(12) Chem istry ............................. 41 VI Statement of the Problem ................................................................. 46 EXPERIMENTAL........................................................................................................ 48 I Apparatus................................................................................................ 48 II Reagents ............................................................................................ 52 III Solvents 55 . IV Preparation of Starting Materials ................................................. 58 TABLE OF CONTENTS (continued) Page V Reactions . 67 A. Deprotonation of Hexaborane(lO) Derivatives .... 67 B. Relative Acidities of the Bora ne s ....................................... 68 C. Preparation of KBgH^^................................................................. 68 D. Preparation of KBgHj^j^ from B g H ^ g..................................... 69 E. Preparation of ByH 22 and CHgByH^^ Salts ................. 70 F. Tensimetric Titration of [(n"C: 4 Hg)^N^] [a-CHgBgHg"] with BgHg......................................................... 71 G. Protonation of CHgByH^^" .................................................... 71 RESULTS AND DISCUSSION................................................................................ 72 I NMR Spectra of K'^[2-BrBgHgl..................................................... 72 II NMR Spectra of K+[2-CHgBgHgl........................ 77 III NMR Spectra of K'*‘[2 , 3 -(CH 3 )2 B6 H7 ] ........................... • 85 IV Relative Acidities of 2-BrBgHg and 2-CHgBgHg with Respect to B gH ig.................................................................... 90 V NMR Spectra of KBgH^..................................................................... 93 VI Deprotonation of BgH]^2 ..................................................................... 101 VII NMR Spectra of B7 H1 2 ................................................ 103 VIII NMR Spectra of CH3 B7 H1 1 ............................................................ I l l REFERENCES........................................................................................................... 119 Vi LIST OF TABLES Table Page 1 NMR Data for Hexaborane(lO).................................................... 6 2 NMR Data for KBgHg........................................................................ 10 3 NMR Data for BsHn'^Br" ................................................................ II 4 NMR Data for 2-Bromohexaborane(10)..................................... 15 5 NMR Data for 2-Methylhexaborane(10) ................................. 20 6 NMR Data for 2 -CH 2 BgHio"^Br"................................................ 23 7 NMR Data for 2 ,3-Dimethylhexaborane(10) ......................... 26 8 NMR Data for KB^Hg........................................................................ 28 9 NMR Data for K+[2-CHgBgHyl................................................ 35 10 NMR Data for Hexaborane(12).................................................... 45 11 NMR Data for K'*'[2-BrBgHgl........................................................ 74 12 NMR Data for K+[2 -CH 3 BgHg“] ................................................ 79 13 NMR Data for K+[2 , 3 -(CHg)2 BgHy-]....................’ .................. 87 14 NMR Data for KBgH^i........................... 95 vii LIST OF FIGURES Figure Page 1 Molecular Structure of Hexaborane(lO) ...................................... 3 2 Valence Structure of Hexaborane(lO) .......................................... 3 3 Variable Temperature Boron-11 NMR Spectrum o fB e H lO ................................................................................................ 7 4 Variable Temperature Proton NMR Spectrum of « « « 8 5 Mechanism of the Bridging Hydrogen Tautomerism