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INFORMATION to USERS the Most Advanced Technology Has Been Used to Photo­ Graph and Reproduce This Manuscript from the Microfilm Master INFORMATION TO USERS The most advanced technology has been used to photo­ graph and reproduce this manuscript from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. 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University Microfilms International A Bell & Howell Information Company 300 North Zeeb Road, Ann Arbor, Ml 48106-1346 USA 313/761-4700 800/521-0600 Order Number 0011152 Chemistry derived from the tetracarbonylates of group 8, [M(CO)4]2- (M = Fe, Ru, Os): Syntheses, characterization and derivative chemistry of the metalladiboranes, [M(CO )4 (j7 2-B 2 Hs)]~ (M = Ru, Os). Syntheses and structure of the heterobinuclear dianions of the iron triad, [MM'(CO)s]2~ (MM* = FeRu, RuOs, FeOs) Cofly, Tim Joseph, Ph.D. The Ohio State University, 1989 300N.ZeebRd. Ann Arbor, MI 48106 Chemistry Derived from the Tetracarbonylates of Group 8, [M (C O )4]2- (M = Fe, Ru, Os): Syntheses, Characterization and Derivative Chemistry of the M etalladiboranes, [M(CO)4(-q2-B2H5)]* (M = Ru, Os). Syntheses and Structure of the Heterobinuclear Dianions of the Iron Triad, [MM'(CO)8]2- (MM' = FeRu, RuOs, FeOs). 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 Tim J. Coffy, B. S. The Ohio State University 1989 Dissertation Committee Dr. Bruce E. Bursten Dr. James A. Cowan A dviser Dr. Sheldon G. Shore Department of Chemistry To Annamary and Eric ii Acknowledgements I would like to acknowledge the Department of Chemistry, the National Science Foundation and B. P. America for their financial support. I am grateful to Professor Sheldon G. Shore for his patience, guidence, and support through the duration of this project. I would like to thank the Shore group members, past and present, for many helpful discussions. I would also like to thank Dr. William Quintana for solving a crystal structure presented in this work and for his invaluable assistance in preparing this dissertation. I am indebted to Ms. Therese Salupo for solving a crystal structure presented in this dissertation. I am especially grateful to my wife, Annamary, for her love, patience, understanding and unyielding support during this trying time. Finally, I want to thank my son, Eric Michael, for having impecable timing and for his company during the preparation of this dissertation. V ita August 5, 1962 Bom - Titisville, FL. 1984 B. S. (Chemistry), The University of Pittsburgh. 1984 - 1986 Graduate Teaching Associate, Department of Chemistry, The Ohio State University, Columbus, OH 1986 - 1988 Graduate Research Associate, Department of Chemistry, The Ohio State University, Columbus, OH 1988 - 1989 Graduate Fellow, B. P. America, Department of Chemistry, The Ohio State University, Columbus, OH Publications "Decacarbonyl (t|5-Cyclopentadienyl) Dihydrido Cobalt Triosmium CoOs3(p- H)2Cn^-C5H5)(n-CO)(CO)9. Nonacarbonyl (t\^-Cyclopentadieny 1) Trihydrido and (ri^-Cyclopentadienyl) Tetrahydrido Cobalt Triosmium CoOs3(m-H)3(h5- C5Hs)(CO)9 and CoOs3(|i-H)4(Ti5-C5H5)(CO)9", Jan D.-Y.; Coffy, T.J.; Hsu, W.-L.; Shore, S.G., Inorganic Synthesis, 1989, 25, 195. "Ruthenium and Osmium Bridged Diborane (6) Derivatives [(p-M(CO)4)B2H5]‘ M=Ru,Os.", Coffy, T.J.; Shore, S.G., Abstracts from the 194th meeting of the American Chemical Society, New Orleans, Inor 158. "Reactivity of the Metalladiboranes [M(CO)4(ti2-B2H5)]‘ M = Fe, Ru, Os." Coffy, T. J.; Shore, S. G. Abstracts from the 25th regonal Meeting of the American Chemical Society, Cleveland, OH. iv "Borane Assisted Transition Metal Cluster Chemistry.", Shore, S.G.; Coffy, T.; Jan, D.-Y.; Krause, J.; Workman, D., Abstracts from the 195th meeting of the American Chemical Society, Toronto, Canada, Inor 705. "Borane Assisted Transition Metal Cluster Chemistry.", Shore, S.G.; Coffy, T.; Jan, D.-Y.; Krause, J.; Workman, D., Abstracts from the First Boron Workshop (BUSA-1), Southern Methodist University, Dallas, Texas, MM4. Fields of Study Major Field: Inorganic Chemistry Studies in Nonmetal and Organometallic Chemistry. Professors Bruce E. Bursten, Daryle H. Busch, Daniel L. Leussing, Devon W. Meek, Eugene P. Schram, Sheldon G. Shore, Andrew Wojcicki. V Table of Contents Dedication ............................................................................................................................ ii Acknowledgements ............................................................................................................. iii Vita..........................................................................................................................................iv List of Tables..................................................................................................................... x List of Figures................................................................................................................... xi Chapter Page I. Introduction ........................................................................................................... 1 A. Transition Metal Carbonylates ......................................................................... 1 1. Synthesis of [M(CO)4]2' (M = Ru, Os) ...................................................... 4 2. Chemistry of [M(CO)4]2' (M = Ru, Os) ...................................................... 5 a. Reactions of [M(CO)4]2* (M = Ru, Os) with Charged Electrophiles............................................................................ 5 b. Reactions of [M(CO)4]2‘ (M = Ru, Os) with Neutral Electrophiles............................................................................. 13 B. Metallaborane Chemistry ................................................................................... 18 1. (n2-B2H5) Compounds ....................................................................................20 2. (n3-B2H5) Compounds .................................................................................. 25 3. B2H x (x= 6 or 7) Compounds .......................................................................27 II. Results...................................................................................................................... 35 A. Reactions of Organometallic Anions with Diborane .............................. 35 1. Preparation and Characterization of K[M(CO)4(ti2-B2H5)] (M = Ru, Os).................................................................................................. 35 2. Preparation and Characterization of (n5-C5H5)Ru(CO)2(Tl2-B2H5)] ................................................................. 51 3. Synthesis of K[Cr(CO)4B3Hg] from K2[Cr(CO)s] and THFBH3 59 4. The Reaction of Other Anions with Diborane ..................................... 62 B. Reactivity of K[M(CO)4Cn2-B2Hs)] (M = Fe, Ru, Os) ............................... 63 1. Synthesis of HM(CO)4(ti2-B2H5) (M = Ru, Os) .................................... 63 2. Synthesis of (CH3)Os(CO)40l2-B2H5) ................................................... 74 3. Synthesis of (Ph3PAu)M(CO)4Cn2-B2Hs) M = Fe, Ru, Os ................. 78 4. The Reaction Of [Os(CO)4(ti2-B2H5)]' with Other Organometallic Halides ................................................................................ 86 5. The Reaction of PPN[Os(CO)4Cn2-B2H5)] with (p-H)2Os3(CO)io......................................................................................... 86 6. The reaction of [Os(CO)4(ti2-B2H5)]‘ with Cr(CO)6 ......................... 87 7. The reactions of [Os(CO)4(ti2-B2H5)]' with Lewis Bases ................ 88 C. The Synthesis, Characterization and Structure of Group 8 Bimetallic Dianions .......................................................................... 91 1. Synthesis of Na2[Os2(CO)s] ........................................................................ 91 2. Heterobinuclear Group 8 Dianions [MM’(CO)g]2' (MM' = FeRu, FeOs, RuOs)........................................................................ 95 III. Discussion .............................................................................................................. 109 A. (q2-B2H5) Compounds..... ................................................................................. 109 1. Synthesis of K[M(CO)4(ti2-B2H5)]
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