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Information to Users INFORMATION TO USERS While the most advanced technology has been used to photograph and reproduce this manuscript, the quality of the reproduction is heavily dependent upon the quality of the material submitted. For example: • Manuscript pages may have indistinct print. In such cases, the best available copy has been filmed. • Manuscripts may not always be complete. In such cases, a note will indicate that it is not possible to obtain missing pages. • Copyrighted material may have been removed from the manuscript. In such cases, a note w ill indicate the deletion. Oversize materials (e.g., maps, drawings, and charts) are photographed by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. Each oversize page is also filmed as one exposure and is available, for an additional charge, as a standard 35mm slide or as a 17”x 23” black and white photographic print. Most photographs reproduce acceptably on positive microfilm or microfiche but lack the clarity on xerographic copies made from the microfilm. For an additional charge, 35mm slides of 6”x 9” black and white photographic prints are available for any photographs or illustrations that cannot be reproduced satisfactorily by xerography. 8703628 Wermer, Joseph Raymond PREPARATION AND REACTIONS OF ANIONS DERIVED FROM PENTABORANE(9); PREPARATION OF NEW METALLABORANES Ohio University Ph.D. 1986 University Microfilms International 300 N. Zeeb Road, Ann Arbor, Ml 48106 PLEASE NOTE: In all cases this material has been filmed in the best possible way from the available copy. Problems encountered with this document have been identified here with a check mark V . 1. Glossy photographs or pages _____ 2. Colored illustrations, paper or print ______ 3. Photographs with dark background ____ 4. Illustrations are poor copy ______ 5. Pages with black marks, not original copy _____ 6. Print shows through as there is text on both sides of page ______ 7. Indistinct, broken or small print on several pages 8. Print exceeds margin requirements _____ 9. Tightly bound copy with print lost in spine_______ 10. Computer printout pages with indistinct print ______ 11. Page(s) ____________lacking when material received, and not available from school or author. 12. Page(s) ____________seem to be missing in numbering only as text follows. 13. Two pages numbered . Text follows. 14. Curling and wrinkled pages _ 15. Dissertation contains pages with print at a slant, filmed as received ______ 16. Other___________________________________________________________________ University Microfilms International PREPARATION AND REACTIONS OF ANIONS DERIVED FROM PENTABORANE(9 ); PREPARATION OF NEW METALLABORANES DISSERTATION Presented in Partial Fulfillment of the Requirements for The Degree of Doctor of Philosophy in the Graduate School o f the Ohio State U niversity By Joseph Raymond Wermer, B.A., M.S. The Ohio State U niversity 1986 Reading Committee: Approved by: Dr. Eugene P. Schram Dr. Daniel L. Leussing Dr. Sheldon G. Shore Advisor Department of Chemistry to Mary, Michael Joseph and Daniel John i i ACKNOWLEDGEMENTS I wish to thank the Army Research Office, Durham, North Carolina for financial support. I also wish to thank Professor Shore for his help and guidance in this project. I am especially thankful to my wife, Mary, for her understanding support during my graduate studies. Special thanks are also extended to Dr. Steven Lawrence and Mr. Thomas Getman who helped me a great deal with my research. I wish also to acknowledge the help o f other members of the Shore research group, especially Ms. Jeanette Krause who helped me to prepare th is manuscript. Finally, I wish to thank Kathy Curry for her patience in typing this dissertation. VITA November 5, 1954 Born - M ontpelier, Ohio 1978 B.A. (German), The College of Wooster, Wooster, Ohio 1979-1980 Graduate Teaching Associate, Department of German, The Ohio State U nive rsity, Columbus, Ohio 1980-1983 Graduate Teaching Associate, Department of Chemistry, The Ohio State U n ive rsity, Columbus, Ohio 1983-1986 Graduate Research Associate, Department of Chemistry, The Ohio State U n ive rsity, Columbus, Ohio 1984 M.S. (Chemistry), The Ohio State U n ive rsity, Columbus, Ohio PUBLICATIONS Wermer, J. R.; Shore, S. G. "Classical Pentaborane(9) Chemistry for the Preparation of Higher Boron Hydride Systems; Some New Aspects of the Chemistry of Pentaborane(9) and Decaborane(14)," Molecular Structures and Emergencies, accepted for publication. Wermer, J. R.; Hosmane, N. S.; Siriwardane, U.; Alexander, J. J.; Shore, S. G. "Synthesis and X-ray Crystal Structure of arachno- 6 - ((CH3)3Si )-6,9-CoBqH 1 3 through a Cage-Expansion Reaction o f jTi_do- 2,3-((CH?)3 Si)g-2,3-CgB/|H6," Inorg. Chem., 1986, 25, 4351. Lawrence, S. H.; Wermer, J. R.; Boocock, S. K.; Banks, M. A .; K e lle r, P. C.; Shore, S. G. "Pentaborane(9) as a Source fo r Higher Boron Hydride Systems. A New Synthesis o f nido- 5 , 6 -(CH<j)9 - 5 , 6 -C9 BHHin ," Inorg. Chem. 1986, 25, 367. iv VITA (CONTINUED) FIELDS OF STUDY Major Field: Inorganic Chemistry Studies in Non-Metal and Organometal1ic Chemistry: Professors Sheldon G. Shore, Eugene P. Schram, and Andrew W ojcicki. Studies in Transition Metal and Bioinorganic Chemistry: Professors Daryle H. Busch, Bruce E. Burster, Daniel L. Leussing, and Devon W. Meek. v TABLE OF CONTENTS Page DEDICATION i i ACKNOWLEDGEMENTS i i i VITA iv LIST OF TABLES x LIST OF FIGURES xi LIST OF ABBREVIATIONS xiv INTRODUCTION 1 I. H isto rica l Background to the Preparation of the Boron Hydrides. 1 I I . P ractical Syntheses o f Tetraborane(lO), Pentaborane(ll), Hexaborane(lO), and Decaborane(14). 3 III. Physical Properties and Stabilities of the Boron Hydrides. 6 IV. Structures of the Boron Hydrides. 8 V. Bronsted Acidities of the Boron Hydrides. 11 VI. The Chemistry of Pentaborane(9). 13 A. Reactions w ith Lewis Bases. 13 B. Reactions w ith Strong Bronsted Bases. 14 C. Halogenation and Alkylation Reactions. 18 D. Reaction of Pentaborane(9) with Alkali Metals. 24 v i V II. Statement o f the Problem. 2b RESULTS AND DISCUSSION 28 I. Reduction of Pentaborane(9) with Alkali Metals to Form the Nonahydropentaborate(2-) Dianion. 28 A. Preparation and Characterization. 28 B. Protonation of LB^Hy]2“ with HC1 and HBr. 3b C. Reaction of LBgHg]^- w ith B£Hg and BgHg. 39 D. Other Reactions of Alkali Metal Napthalides and Pentaborane(9). 42 II. Production of the Tetradecahydrononaborate(l-) Anion from Deprotonation Reactions of Pentaborane(9) 44 A. Reaction of Pentaborane(9) with Sodium and Potassium Hydride. 44 B. The Reaction of Pentaborane(9) with the Borohydride Ion. 55 C. Preparation of the Tetradecahydrononaborate(l-) anion from Pentaborane(9). 60 D. The Preparation of Decaborane(14) from Pentaborane(9). 62 E. Preparation of j]j-0ctadecaborane(22) from Pentaborane(9). 6 8 F. Other Related Reactions. 69 III. Formation of Triosmium Carbonyl Methylidyne D erivatives o f Boranes and Carboranes. 71 A. Preparation of Derivatives of Pentaborane(9) 71 B. Preparation of Derivatives of Decaborane(14) 76 C. Preparation of Derivatives of ^-Carborane 78 EXPERIMENTAL 8 b I . Apparatus and Equipment. 85 A. Vacuum Line. 8 b B. Dry Box. 8 6 v ii C. Reaction vessels. 8 6 D. Nuclear Magnetic Resonance Spectra. 87 E. Mass Spectra 90 F. Infrared Spectra. 90 G. High Pressure Liquid Chromatography. 91 I I . Reagents. 91 III. Reactions. 96 A. Reaction of B^Hg w ith two equivalents o f potassium napthalide. 96 B. Preparation o f the crown ether complex [K(dibenzo-18-crown-6)]2B5Hg. 97 C. "One-pot synthesis" o f BgHji from K 2 [BgHg] by protonation with HC1 in Butane. 97 D. Preparation of ®5«U from C s2[B 5H g ] by protonation with liquid HC1. 98 E. Preparation of B 5 H jj from K 2 [B 5 Hg] by protonation with liquid HBr. 99 F. Reaction of BcHg with 1 equivalent of Na+(CioH8r . 100 G. Reaction of BcHg with 1/2 equivalent of Na+(cioH8)‘ . 1 0 0 H. Low Temperture Reaction of [(n-C/iHobNXBcHo] w ith B5 Hg. 101 I. Low Temperature Reaction o f K[BgHg] with B^Hg. 102 J. Reaction of B^Hg with Li[BH^]. 102 K. Preparation of K[Bj j H ^ ] from B^Hg. 103 L. Attempt to prepare K[BiiH^] by a stoichiometric reaction of BgHg with Kfl. 104 M. Preparation of B^H 2 2 isomers from CB^H^]". 104 N. Improved preparation of B^qH ^ from B^Hg. 10b 0. Preparation of ^v-B^gH 2 2 from BgHg. 109 v i i i P. Reaction of BgH^Q with one-half equivalent of KH in glyme. 1 1 0 Q. Preparation of (u-H) 3 (C0 )g 0 s 3 (p^-C-l-B^Hg). Ill R. Preparation of (u-H^COjgOs^p-j-C-^BgHj^). 112 LIST OF REFERENCES 114 ix LIST OF TABLES Table Page 1. Some physical properties of selected boron hydrides. 7 2. A Comparison of Properties and Reactivities of [BjjHg] and [BgHg] . 3 4 3. Boron-11 NMR Chemical S h ifts , Coupling Constants and Assignments 9 for jr-BjgF^. 107 4. Boron-11 NMR Chemical S h ifts and Coupling Constants fo r _L~Bi 3 H2 2 - 108 x LIST OF FIGURES Figure Page 1. One possible mechanism fo r polyhedral expansion from diborane( 6 ) pyrolysis. 4 2. Cross-sectional view of a Pyrex hot-cold reactor. 5 3. The molecular structure of diborane( 6 ). 9 4. Structural classes of boron hydride clusters. 12 5. Structures and boron-11 NMR spectra of BcHg and [B5H8r 15 6 .
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