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INFORMATION to USERS Universiw M Icrxjfilm S Internationéil INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1. The sign or “target” for pages apparently lacking from the document photographed is “Missing Page(s)” . If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed. For blurred pages, a good image of the page can be found in the adjacent frame. If copyrighted materials were deleted, a target note will appear listing the pages in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photographed, a definite method of “sectioning” the material has been followed. It is customary to begin filming at the upper left hand comer of a large sheet and to continue from left to right in equal sections with small overlaps. I f necessary, sectioning is continued again—beginning below the first row and continuing on until complete. 4. For illustrations that cannot be satisfactorily reproduced by xerographic means, photographic prints can be purchased at additional cost and inserted into your xerographic copy. These prints are available upon request from the Dissertations Customer Services Department. 5. Some pages in any document may have indistinct print. In all cases the best available copy has been filmed. U niversiW Micrxjfilms Internationéil 300 N. Zeeb Road Ann Arbor, Ml 48106 8311779 Miller, Mark Allen LOW VALENT ALUMINUM COMPOUNDS: REACTIONS AND CHEMISTRY OF TETRAISOBUTYLDIALUMINUM The Ohio State University Ph.D. 1983 University Microfilms I nternationsil 300 n. zeeb R W . Ann Arbor, M I 48106 LOW VALENT ALUMINUM COMPOUNDS: REACTIONS AND CHEMISTRY OF TETRAISOBUTYLDIALUMINUM DISSERTATION Presented in P artial F u lfillm en t of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Mark Allen Miller, B.A., M.S. ***** The Ohio State University 1982 Reading Committee: Approved By Dr. Eugene P. Schram Dr. Sheldon Shore Dr. Andrew Wojcicki Adviser Department o f Chemistry TO MOM 11 ACKNOWLEDGMENTS I would lik e to thank my adviser. Dr. E. P. Schram, fo r his advice and patience throughout my tenure at The Ohio State University. Special thanks to my colleagues. Bill and Drew. I would like to thank my typist, LaDonna Northern, for a splendid job under difficult conditions. i n VITA February 7, 1953 ................. Born - M assillon, Ohio 1975 .......................................... B .A ., The College o f Wooster, Wooster, Ohio 1978 .......................................... M .S ., The Ohio State U n iv ersity, Columbus, Ohio 1975-1981 .............................. Teaching Associate, The Ohio State Uni­ v e rs ity , Columbus, Ohio 1975-1982 Research Associate, The Ohio State Uni­ v e rs ity , Columbus, Ohio FIELDS OF STUDY Major Field: Chemistry IV TABLE OF CONTENTS Page DEDICATION....................................................................................................................... ü ADKNOWLEDGMENTS......................................................................................................... i i i VITA ................................................................................................................................... iv LIST OF TABLES............................................................................... v ii LIST OF FIGURES......................................................................................................... v i i i INTRODUCTION ........................................................................................... 1 EXPERIMENTAL....................................................................................................... 19 Equipment ...................................................................................................... 19 Analyses........................................................................................................... 29 Reagents ........................................................................................................... 30 Purchased Reagents ............................................................................. 30 Prepared Reagents ............................................................................ - 33 Boron Compounds............................................................................. 33 Aluminum Compounds......................................................................... 34 Pentacarbonylmanganese Hydride ................................................ 38 T ris(triphenylphosph1ne) pi a t 1num(0 ) .................................... 39 Reactions of Tetralsobutyldlaluminum ........................ 40 With Protonic Reagents ...................................................... 40 With HCl........................................................................................ 40 With Dimethyl amine ......................................................................... 42 With Ethyl ami n e ....................................................................... 43 With Dimethyl amine Adduct of D1Isobutyl- dimethyl ami noaluminum ................................................................. 44 With Toluene-3,4-D1 th io l .................................................. 45 Reactions w ith Aluminum and Boron Compounds .................................. 46 With T ri methyl aluminum .................. ............................................ 46 Attempted Preparation of Lewis Base Adducts of Tetra 1 s obutyl d 1 al uml num............................................................. 47 With Boron Trichloride ..................................................................... 48 V TABLE OF CONTENTS (c o n t.) Page With Trimethoxyboron ................................................................... 49 With T ri s (dimethyl ami no) boron...................................................... 52 Reactions w ith Transition Metal Compounds .............................. 54 With Dimanganese Decacarbonyl .................................................. 54 With Pentacarbonylmanganese Hydride ...................................... 55 With Tris(triphenylphosphine)platinum(O).......................... 56 RESULTS AND DISCUSSION..................................................................................... 58 Introduction............................................................................................ 58 Reactions with Protonic Reagents ................................................... 63 With H C l............................................................................................ 64 With Dimethyl ami n e ....................................................................... 73 With Ethyl ami ne ............................................................................... 86 With Dimethyl amine Adduct o f Diisobutyldim ethyl- aminoaluminum. ............................................................... 87 With Toluene-3,4-Dithiol ..................... 89 Reactions w ith Aluminum and Boron Compounds .......................... 96 With Trimethyl aluminum ............................................................... 96 Attempts to Prepare Lewis Base Adducts o f T etrai sobutyl di al uminum......................................... T09 ' With Boron Trichloride . ....................................................... 115 With Trim ethoxyboron ................................................................... 118 With Tris(dimethylamino)boron................................................... 142 Reactions with Transition Metal Compounds .............................. 155 • With Dimanganese Decacarbonyl ................................................... 155 With Pentacarbonylmanganese Hydride ...................................... 156 With Tris(triphenylphosphine)platinum (0).......................... 161 SUMMARY.................................................... 167 APPENDIX................................................. 168 LIST OF REFERENCES.................... 188 VI LIST OF TABLES Table Page 1. Infrared Frequencies for Trimethoxyboron. ................................... 170 2. Infrared Frequencies for Tris(dimethylamino)boron ...................172 3. Infrared Frequencies for Tetrai sobutyl dial uminum .......................175 4. Infrared Frequencies for Diisobutylmethoxyaluminum ...................177 5. Infrared Frequencies for Di i sobutyldi methylami noalumi num. 179 6 . In frared Frequencies fo r Pentacarbonylmanganese Hydride . 181 7. Infrared Frequencies for Tris(triphenylphosphine)platinum . 183 8 . Infrared Frequencies for Products of Treatment of Tetraiso­ butyl dial uminum with HCl ... 68 9. Dihydrogen Evolution from Tetraisobutyldialuminum and Dimethylamine at Room Temperature ............................................. 75 10. Dihydrogen Evolution from Tetrai sobutyldialumi num and Dimethyl ami ne at 4 3 °C .....................................................................
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