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University Miaorilms International 300 N 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. 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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. University Miaorilms International 300 N. Zeeb Road Ann Arbor, Ml 48106 8403589 Yu, Yuan-Fu STUDIES ON BINUCLEAR IRON CARBONYL AND NITROSYL COMPLEXES CONTAINING BRIDGING DIPHENYLPHOSPHIDE The Ohio State University Ph.D. 1983 University Microfilms International 300 N. Zeeb Road, Ann Arbor, Ml 48106 Copyright 1983 by Yu, Yuan-Fu All Rights Reserved 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. G lossy photographs or p a g e s_______ 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. Other __________________________________________________________ University Microfilms Internationa! STUDIES ON BINUCLEAR IRON CARBONYL AND NITROSYL COMPLEXES CONTAINING BRIDGING DIPHENYLPHOSPHIDE DISSERTATION Presented in Partial fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Yuan-Fu Yu, M.S * * * * * The Ohio State University 1983 Reading Committee: Approved By Dr. Andrew Wojcicki Dr. Sheldon G. shore Dr. Andrew Wojc Dr. Devon W. Meek Department of THE AUTHOR DEDICATES THIS DISSERTATION TO HIS MOTHER Mrs. Hseuh-Wen Lu Yu ii ACKNOWLEDGMENTS I wish to thank Professor Andrew Wojcicki for his guidance, support, and inspiration during the course of this investigation. I thank Drs. Robert Waid and John Letts for providing invaluable help with the Bruker HX-yO NMK Spectrometer. I also thank Mr. Carl Engelman for his help in obtaining many NMR spectra. I would like to express my gratitude to my parents, my sister, and my brother, whose patience and support are greatly appreciated. I would like to thank my wife, Lucy; without her support and help I would never have made it. VITA November 9, 1954......... Born in Taiwan, Republic of China 1976....................... B.S., Tamkang College of Arts and Science, Tamsui, Taiwan 1976-1978................. M.S., University of Missouri- Kansas City, Kansas City, Missouri 1978-1983................. Teaching and Research Assistant, The Ohio State University, Columbus, Ohio PUBLICATIONS Y.-F. Yu, J. Gallucci and A. Wojcicki, "Novel Mode of Reduction of Phosphido-Bridged, Metal-Metal-Bonded Binuclear Complexes. Synthesis and Reactivity of an Unsymmetrical Anion from Fe2 (C O )6 (p-PPh2 )2 ." J. Amer. Chem. Soc., 1983, 105, 4826. Y.-F. Yu and A. Wojcicki, "New Binuclear Iron Carbonyl and Nitrosyl Complexes." Paper presented to the 1983 National Meeting of the American Chemical Society, Washington, D.C., August, 1983. Y.-F. Yu and A. Wojcicki, "Reduction of [Fe(CO)3 (p-PPh2 ) ]2 and [Fe(NO)2 (p-PPh2)]2 and Reactions2of a New Dianion, [(C O )3F e (p-PPh2 )(p-Co)Fe(C O )2 (PPh2 )] Paper presented to the 1983 15th Central Regional Meeting of the American Chemical Society, Oxford, Ohio, May 23-25, 1983. Y.-F. Yu, A. Wojcicki, G. Nardin and M. Calligaris, "Crystal Structures of [Fe2 (NO)i* (p-PPh2 ) (p-CH2PPh2 ) ] and [ Fe2 (N O ) 1+( P-CH2 ) (p-P2Phif) ] . " Paper presented to the 11th International Conference on Organometallic Chemistry, Pine Mountain, Georgia, October, 1983. FIELDS OF STUDY Major Field: Inorganic Chemistry, Professor Andrew Wojcicki iv TABLE Of CONTENTS Page DEDICATION...................................................... ii ACKNOWLEDGMENTS ............................................. iii VITA............................................................. iv LIST Of TABLES............................................... viii LIST OF FIGURES................................................ xi LIST OF ABBREVIATIONS....................................... xvii I. INTRODUCTION A. General..................................................1 B. Synthesis of organometallic Compounds with Phosphido Bridged Ligands.......................'..... 2 C. The Phosphorus Nuclear Magnetic Resonance Spectroscopy...........................................11 D. Reactions of Metal-Metal Bonded Phosphido- Bridged Compounds..................................... lb E. Application of MBR^H Reagents to Organometallic Chemistry.............................................. 25 F. Research Objective.................................... 28 II. EXPERIMENTAL A. Reagents and Chemicals...............................2y B. Instrumentation and Physical Measurements......... 32 C. General Experimental Procedures.................... 34 D. Preparations of Known Compounds.................... 35 v E. Preparation and Characterization of Starting Materials...................................36 E. Reduction of [Ee ( CO) 3 ( y-PPh2 ) ] 2 an<3 [Ee (N O )2 (y-PPh2 ) ] 2 ...................................39 G. Reactions of the Diphenylphosphine-Substituted Monoanions, [(CO)^Ee(y-PPh2 )(y-Co)E e (C o )2 (PPh2H )]“ and [ (NO)2Ee(y-NO)(y-PPh2 )Ee(NO)(PPh2H)]~.........56 H. Reactions of the Unsymraetrical Dianions,......... 80 I. Reactions of Alkyldiphenylphosphine-Substituted Monoanions, [(CO)3Ee(y-PPh2 )(p-CO)Fe(CO)2 (PPh2R )]” ....................................................... 93 J. X-ray Crystal Structure Determinations.......... 1UU III. RESULTS AND DISCUSSION A. Preparation and Characterization of [Ee (C o )3 (y-PPh2 )]2 and [Fe(NO)2 (y-PPh2 )]2...... 108 B. Reduction of [Fe (CO) 3 (y-PPh2 ) ] 2.................. 114 C. Unsymmetrical Dianion, [ (CO)oEe(y-PPh9)(y - C O ) 2 _ Ee(CO)2PPh2 )] , and its Conversion to [Ee(CO)3 (y-PPh2 ) ] \ ~ ............................... 144 D. Reduction of [ Ee (No) 2 (y-PPh2 )) 2 .................. 155 E. Unsymmetrical Nitrosyl Dianion, [(no)2E e (y - N O ) (y-PPh2)E e (N O )(PPh2 )]2 _ , and its Conversion to [Ee(NO)2 (u-PPh2)]|"............................ 171 E. Reactions of [(CO)3E e (y-PPh2 )(y-CO)Ee(Co)2- (PPh2)]2” with Alkylating Agents and Protonating Agents...,............................ 176 vi G. Reactions of [ (CO)3Fe(p-PPh2)(p-CO)Fe(CO)2 (PPh2H)]~ with Alkylating Agents................238 H. Reactions of [ (CO)3Fe(p-PPh2)(p-CO)Fe(Co)2(PPh2))2~ and [(CO)3Fe(p-PPh2)(p-CO)Fe(CO)2(PPh2H)]- with Trifluoroacetic Acid............................. 245 I. Reactions of [(NO)2Fe(p-PPh2 )(P - N O )F e (N O )(PPh2H )]“ and [(N O )2Fe(p-NO)(p-PPh2 )F e (N o )(PPh2 )]2 " with Alkylating Agents............................ 248 J. Fluxional Behavior of Some Binuclear Iron Carbonyl Complexes.................................268 IV. CONCLUDING REMARKS...................................... 278 APPENDICES A. Selected Bond Angles and Bond Lengths of ((CO)3Fe(p-PPh2)2Fe(PPh2C3H5 )(CO)2]............. 280 B. Variable Temperature ^ P { H> NMR Spectra of [ (CO)3 Fe(p-PPh2 )(p-C(Et)O)Fe(CO)2(PPh2Et)]..... 284 C. Variable Temperature ^ P {^H} NMR Spectra and C NMR Spectra of CO Ligands of [(C O )3 Fe (p-PPh2 )2(p-CO)Fe(Co)2 (PPh2H)]"........ 28 7 D. Variable Temperature ^ C NMR Spectra of the CO Ligands of f(CO)3F e (p-PPh2 )2“ ( p-CO) Fe( CO) 2 ( PPh2Me ) ] ” .......................... 29U BIBLIOGRAPHY.................................................
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