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Xerox University Microfilms 300 North Zoob Road Ann Arbor, Michigan 48106 75-19,451 HOLLANDER, Or1n, 1946- REACTIONS OF AMMONIA WITH DECAB0RANE(14) AND S THE FORMATION OF A STABLE ION-DIPOLE COMPLEX I OF DECABORANE; PREPARATION AND ISOLATION OF TETRACARBONYLIRON HEPTABORANE(ll), ELECTROPHILIC STABILIZATION OF AN UNSTABLE BORON HYDRIDE. The Ohio State University, Ph.D., 1975 Chemistry, Inorganic i ! Xerox University Microfilms Annr Arbor, Michigan 48106 THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED. REACTIONS OF AMMONIA WITH DECABORANE (14) AND THE FORMATION OF A STABLE ION-DIPOLE COMPLEX OF DECABORANE; PREPARATION AND ISOLATION OF TETRACARBONYLIRON HEPTABORANE(11) , ELECTROPHILIC STABILIZATION OF AN UNSTABLE BORON HYDRIDE DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in the Graduate School of The Ohio State University By Orin Hollander, B.A. The Ohio State University 1975 Reading Committee: » Approved by Sheldon G. Shore Daryle H. Busch Gary G. Christoph 7 " Advisor Department of Chemistry ACKNOWLEDGMENTS I would like to express my appreciation for the finan­ cial support of the National Science Foundation, the Conti­ nental Oil Company, and the Department of Chemistry. I am especially grateful to Dr. Sheldon 6 . Shore fot his guidance and suggestions which made these studies pos*- sible. i I deeply appreciate the moral and financial supportj i of my parents, David and Marion. Their continued trust and understanding have been a source of great strength. j I am deeply grateful to my fiance, Terri, for her patience and help in typing the draft of this manuscript.! I especially appreciate the many helpful discussion^ i and suggestions of Dr. Vincent T. Brice and my roommate I Dr. Ihor Jaworiwsky, a Uniquely Knowledgeable Experimental­ ist. i ji ■ i i ii VITA April 15, 1946 ......... Born - Chicago, Illinois 1968 ................... B.A., Northwestern University, Evanston, Illinois 1969-1971 .............. Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1971-1972 ............ Continental Oil Fellow, The Ohio State University, Columbus, Ohio 1970-1975 .............. Research Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio Publications Metalloboranes Derived from the Lower Boron Hydrides, S.G. Shore, D.L. Denton, V.T. Brice, R.K. Hertz, and Orin Hol­ lander, International Boron Symposium, Leeds, England (1974). Preparation and Properties of a Stable Ion-Dipole Complex of Decaborane (14) , B^H,.!” ; Reactions of Decaborane with Ammonia, 0. Hollander ana S.G. Shore, Abstr. Papers, 166th Meeting Amer. Chem. Soc., Chicago, Illinois (1973). Electrophilic Stabilization of an Unstable Boron Hydride: Preparation and Isolation of B 7H.,Fe(CO)4 , 0. Hollander and S.G. Shore, Abstr. Papers, 167th Meeting Amer. Chem. Soc., Los Angeles, Calif. (1974). Preparation, Isolation, and Structure of (C.Hg),jN+ y-Fe(CO)^- B-Hi j ** ?Preparation and Isolation of B^H^-jFe(CO) Electro- pnillc Stabilization of Heptaborane Speca.es, 0. Hollander, W.R. Clayton, and S.G. Shore, Chem. Comm., 604 (1974). Fields of Study Major Field: Inorganic Chemistry iii Studies in Non-metal Chemistry: Professors Sheldon G. Shore and Eugene P. Schram Studies in Transition Metal Chemistry: Professors Daryle H. Busch, Devon W. Meek, and Andrew A. Wojcicki TABLE OP CONTENTS Page ACKNOWLEDGMENTS .................................... ii VITA ................................................ i U TABLES ..................... vii ILLUSTRATIONS ................................... viii INTRODUCTION ....................................... 1 Decaborane(14) ............................... 1 Hexaborane(10) ............................... 12 Metalloboranes ............................... 21 Heptaborane .................................. 37 EXPERIMENTAL ....................................... 43 I. Apparatus and Procedure.............. 42 II. Starting Materials ................... 51 III. Analytical Procedures ................ 33 IV. Reactions of NH3 with B1QH14 ......... 56 V. Reactions of BioH14 w*th ^C4H9^4NI and (C6H5)3PCH3I ...................... 63 VI. Studies of p-Fe (CO) 4-B6H1(J ........... 72 CONCLUSIONS AND DISCUSSION ........................ 93 I. Reactions of Ammonia with Decaborane .. 93 II. Reactions of BinH,,. with (C.Hq).NI and (c6h5)3pch3i 100 Page III. Studies of p-Fe(CO)4-B6H 10 ......... Ill REFERENCES ...................................... 146 vi TABLES Table Page 1. Electron Charge Densities for B^qH^4 ....... 6 2. X-ray Powder Diffraction Data for B10H1 2 (NH3>2 ............................... 3. X-ray Powder Diffraction Data for 1<C6H5)3PCH3 K B 10H10D4I]..................... 69 4. X-ray Powder Diffraction Data for [ CC4H9) 4N 1 tp-Fe (CO) 4“B6H9 1................... 79 5. X-ray Powder Diffraction Data for [<C4H9)4N] [p-Fe(CO)4—B7H12].................... 82 6. Mass-Spectral Data for Fe(CO) 87 7. Mass-Spectral Data for M-Fe(CO)4-2-CH3B6H9 ........................ 90 8. Boron-11 NMR Data for B1QH,4 and ...............7..7................. 96 10 13 9. Boron-11 NMR Data for B1QH14l” Complexes ... 106 10. Boron-11 NMR Data for Iron-Hexaborane(lO) Complexes ................... 125 11. Infrared Data for Iron-Hexaborane(10) Complexes 132 vii ILLUSTRATIONS Figure “ Page 1 Molecular Structure o£ B^oH14 ............ ^ 2 Boron-11 NMR Spectrum of B^qH^4 ......... 4 3 Structure of B2.0H142~ .................... 4 Boron-11 NMR Spectrum of B 10H12 <C2H5NC> 2 ............................. 10 5 Structure of .................... 6 Molecular Structure of BgH10 ................ 14 7 Static Structures for 2-CH^Bf-Hg and 2-BrBgHg ............ 7 . : . ? ........... 24 8 Structure of Beryllium Borohydride ...... 24 9 Structure of B3H g ~ ....................... 30 10 Structure of (CH3) 2AlB3Hg ................ 3® 11 Structure of Mn(CO)3B3Hg ................ 32 12 Structure of [ (CgHg) ^^PtB-jH^ .......... 32 13 Structure of Mn(CO)3BgH^2 ............... 33 14 Topological Structure of B^H^1 ............. 38 15 Tensimetrie Titration Apparatus ............ 47 16 Infrared Spectrum of B^qH^ (NH3) 2 59 17 Boron-11 NMR'Spectrum of B10H12(NH3>2 ................................ 61 18. Infrared Spectrum of [(CcHc)«PCHi] W l O ^ O 0*1!....................... 67 viii Page 19. Boron-11 NMR Spectrum of t <C6Hs> 3PCH3][b10h13] ................... 71 20. Tensimetric plot of the addition- of B2H6 to K [y-Fe(CO)4-B6H9'] in ether .... 75 21. Infrared Spectrum of I(C.HQ).N) [y-Fe(CO)4-B6H9] ............ 78 22. Tensimetric plot of the addition of B-H, to (C4H9)4N y-Fe(GO)4-B6H9 in CH2C12 .... 80 23. Infrared Spectrum of [(C.Hq).N] [U-Fe(CO)4-B7H12] ........... 81 24. Infrared Spectrum of B7H^Fe(CO)4....... 85 25. Infrared Spectrum of p-Fe(CO)4-2-CH3B6H9 ..................... 59 26. Boron-11 NMR Spectrum of [NH4][B1qH13] ........................... 94 27. Boron-11 NMR Spectrum of KB3qH13 ....... 95 28. Boron-11 NMR Spectrum of 1,2,3,4-B10H1qD4 102 29. Boron-ll NMR Spectrum of [(C4H9> 4N][B10H10D4I] ................... 103 30. Boron-11 NMR Spectrum of [(C6H5)3PCH3][B10H10D4I] ............... 104 31. 80.2 Mhz. Boron-11 NMR Spectrum Of t(C4H9)4N][B10H10D4I] ................ 105 32. Raman Spectrum of B 1QH14 and I 3PCH3 J [BiqH,^] in the Terminal B-H ancl Bridging B-H-B region ............................ 108 33. Proposed Structure of B10H14I- Complex ........................ 109 34. Boron-11 NMR Spectrum of yi—Fe(CO)4~BgH3Q 112 ix Page 35. Temperature-dependent boron-11 nmr spectrum of K [p-Fe CCO) b6 h9 " 1 ....................... 113 36. Possible static structures for p-Fe(CO)4-B6H9" ....................

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