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Ml 48106-1346 USA 313/761-4700 800/521-0600 REACTION CHEMISTRY OF FISCHER-TYPE RHENACYCLOBUTADIENE AND t|3-TRIMETHYLENEMETHANE PLATINUM COMPLEXES 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 Vdronique Plantevin The Ohio State University 1995 Dissertation Committee: Approved by: Dr. Bruce Bursten Dr. Viresh Rawal « - Dr. Andrew Wojcicki Adviser / Department of Chemistry UMI Number: 9526075 UMI Microform 9526075 Copyright 1995, by UMI Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. UMI 300 North Zeeb Road Ann Arbor, MI 48103 To My Parents ii ACKNOWLEDGMENT I would like to express my sincere gratitude to my advisor, Professor A. Wojcicki, for his support and guidance. The completion of my experimental work would have been impossible without the collaboration of Carl Engleman (NMR), David Chang (mass spectrometry), and Judith Gallucci (X-ray diffraction analysis). I would like to acknowledge as well the financial support provided by The Ohio State University and the Lubrizol Co. for a graduate fellowship. Thanks to all the members of the Wojcicki group, past and present: Laura L. Padolik, Patrick W. Blosser, Richard R. Willis, Dean E. Rende, Mark W. Baize, Todd R. Dunsizer, Kirsten L. Daniel, and Christopher M. Beck. In addition to constructive chemistry-related discussions, I am appreciative of their moral support and friendship. Finally, I would like to express my gratitude to my parents whose love, patience, and unconditional support have contributed to the completion of my graduate studies. This dissertation is dedicated to them. VITA January 29, 1968 Bom, Rognac, France 1985 Baccalaurdat C, Lycde Vauvenargues, Aix-en-Provence, France 1985-1987 Mathdmatiques Supdrieures-Mathdmatiques Spdciales, Lycde Paul Cdzanne, Aix-en-Provence, France 1987-1989 ESCIL, Lyon, France 1989-1993 Teaching Assistant and Research Assistant The Ohio State University 1994 Lubrizol, Co. Industrial Fellow, The Ohio State University PUBLICATIONS - Plantevin, V.; Blosser, P. W.; Gallucci, J. C.; Wojcicki, A. "ti3-Trimethylenemethane Complexes of Platinum", OrganometaUics 1 9 9 4 , 13, 3651. - Plantevin, V.; Gallucci, J. C.; Wojcicki, A. Inorg. Chim. Acta 1994, 222, 199. FIELDS OF STUDY Major Field: Chemistry Studies in Organic Chemistry Professor Andrew Wojcicki iv TABLE OF CONTENTS DEDICATION............................................................................................................ ii ACKNOWLEDGMENT...............................................................................................iii VITA.............................................................................................................................iv LIST OF TABLES..................................................................................................... vii LIST OF FIGURES.................................................................................................... viii LIST OF SCHEMES...................................................................................................x CHAPTER PAGE I. INTRODUCTION ................................................................................................ 1 PART A: ORGANORHENIUM COMPLEXES........................................... 2 I- Fischer-type carbene complexes ........................................ 2 II- Schrock-type metallacyclobutadiene complexes ............... 19 III- Fischer-type rhenacyclobutadiene complexes .................21 IV- Objectives of the project ................................................... 25 PART B: ORGANOPLATINUM COMPLEXES...........................................26 I- T)3-Propargyl transition metal complexes ...........................26 II- Use of trimethylenemethane transition metal complexes in organic synthesis................................................................32 III- ti3-Trimethylenemethane complexes of platinum ........... 42 IV- Objectives of the project ................................................... 42 II. DISCUSSION ................................................................................................. 44 PART A: ORGANORHENIUM COMPLEXES............................................ 44 I- Fischer-type properties o f .................................................. rhenacyclobutadiene complexes 1 ...........................................44 II- Attempts to diversify die substitution pattern onthemetallacycle .................................................................. 53 III- Exploration of the novel reaction chemistry of rhenacyclobutadiene complexes ..............................................70 IV-Summar y.......................................................................... 132 v PART B: ORGANOPLATINUM COMPLEXES............................................133 I- Spectroscopic data ................................................................133 II- X-Ray diffraction analysis of complex 7 8 ........................ 137 III- Reactivity of complex 7 8 with unsaturated reagents 144 IV- Attempt to change the nature of the substituent on C 2 163 V- Attempts to change the terminal substituent ........................168 VI- Study of the reactivity of complex 150 toward olefins ...................................................................188 VII- Summary......................................................................... 192 III. EXPERIMENTAL PART.................................................................................... 193 PART A: GENERAL PROCEDURES............................................................193 I- General experimental conditions .......................................... 193 II- Instrumentation ...................................................................194 III- Reagents and chemicals ..................................................... 196 PART B: ORGANORHENIUM COMPLEXES.............................................197 I- Preparation of rhenacyclobutadiene complexes ...................197 II- Deprotonation of complex la and deuteration/alkylation studies ..................................................203 III- Aminolysis reactions .........................................................207 IV- Reactions involving P(CH 3 )2Ph ....................................... 210 V- Rhenium cyclopentadienyl complexes ...............................213 VI- Oxygen-atom insertion reactions ....................................... 222 VII- Nucleophilic attack by carbanions ...................................224 VIII- Rearrangements in organonitriles and pyridine .............227 IX- NH-Insertion reactions .....................................................230 PART C: ORGANOPLATINUM COMPLEXES........................................... 236 I- Synthesis of propargyl tosylate starting materials .............. 236 II- Attempts to isolate -propargyl Pt tosylate complexes ................................................................................238 III- Synthesis of various heteroatom-substituted platinum allyl complexes .........................................................240 IV- Synthesis of various trimethylenemethane complexes of platinum ...............................................................................245 V- Reactivity of substituted trimethylenemethane complexes of platinum .............................................................251 REFERENCES.............................................................................................................257 APPENDIX.................................................................................................................. 272 vi LIST OF TABLES TABLE PAGE 1. Product ratios: naphthols versus indenones ......................................... 19 2. Selected 13C{ 1H} NMR chemical shifts of complexes 1 .....................22 3. IR data of complex la and its conjugated base .....................................49 4. Selected 13C{ 1H} NMR chemical shifts of complexes 8 7 ..................57 5. Chelation