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Studies of the Sulfur Dioxide Insertion of Some Metal Complexes

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Studies of the Sulfur Dioxide Insertion of Some Metal Complexes This dissertation has been microiihned exactly as received 66-6231 BIBLER, Jane Pycraft, 1939- STUDIES OF THE SULFUR DIOXIDE INSERTION OF SOME METAL COMPLEXES. The Ohio State University, Ph.D., 1965 Chemistry, inorganic University Microfilms, Inc., Ann Arbor, Michigan STUDIES 0F THE SULFUR DIOXIDE INSERTION OF SOME METAL COMPLEXES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Jane1 Pyc raft Bible-r, A.B., M.S. The Ohio State University 1965 Approved by (a )w a a *& u Advise/ Department of Chemistry ACKNOWLEDGMENTS The successful completion of this study is a direct reflection of the efforts of several groups who have con­ tributed sppport in various ways during my graduate career. In particular, I have selected three which have been most instrumental in the progress of this work. First, I wish to express my appreciation to my family for their patience and understanding. Specifically, I thank my husband, Ned, for his devotion and advice, and my mother, Mrs, Pauline Pycraft, for typing the first and final drafts of this dissertation. Second, I am indebted to the responsible members of the scientific community who, throughout my studies, have provided encouragement and guidance, I especially thank Dr. A, A. Wojcicki, my adviser, for his assistance and counsel during the course of the research and in the pre­ paration of this manuscript. Finally, I wish to acknowledge the financial support of The Ohio State University and the Petroleum Research Foundation, VITA June 3» 1939 «... Born — Lorain, Ohio 1961 . ............ A«B., Miami University, Oxford, Ohio. 1961-1963 ........ Teaching Assistant, Department of Chemistry, The Ohio State University, C olumbus, Ohio. 1963-1965 ........ Research Fellow, Department of Chemistry, The Ohio State University, C olumbus, Ohio. 1 9 6 4 ............. M.S., The Ohio State University, C olumbus, Ohio. PUBLICATIONS J.P. Bibler and A. Wojcicki, J, Am. Chem. Soc., 8 6 , 5051 (1964) FIELDS OF STUDY Major field; Inorganic Chemistry. Dr. Andrew A. Wojcicki iii CONTENTS Page ACKNOWLEDGMENTS............................... ii VITA ......................................... iii PUBLICATIONS ......................... iii FIELDS OF STUDY ............................... iii TABLES ....................................... v FIGURES . / ................................. vii INTRODUCTION ................................. 1 EXPERIMENTAL ................................. 28 Starting materials Preparation of sulfonyl derivatives Preparation of acetyl derivatives of 7t-C5 H5 Fe(CO)2 CH3 Reactions of sulfonyl compounds RESULTS AND DISCUSSION ..................... 101 Investigation of the sulfonyl derivatives Investigation of the acetyl derivatives of tc-C5 Fe(CO)2 CH3 CONCLUSION ................................... 180 APPENDIX I ................................... 182 APPENDIX I I ................................... 203 APPENDIX I I I ................. 208 BIBLIOGRAPHY ................. 211 TABLES Table Page 1. Infrared Frequencies of Free and Coordinated S02 ........................... 24 2. Analyses for Iron and Molybdenum Sulfonyl Derivatives ..................... 64 3. Analyses for Mercury Sulfonyl Derivatives............................... 69 4. Analyses for Acetyl Derivatives of ti-Cj H5 Fe(C0 )2,CH3 ....................... 87 5. Some Physical Properties of Iron and Molybdenum Sulfonyls ..................... 110 6 . Proton Magnetic Resonance Spectra of H-C5 H5 FeCC0)2> R ............................. 112 7. Cyclopentadienyl Proton Chemical Shift Position for it—C5 Fe{C0)2 S02 R .............. 115 8 . Infrared SO Stretching Frequencies of Some Sulfonyl Compounds ................... 120 9® Comparison of Infrared Absorption Fre­ quencies of Tt-C5 H5 Fe(C0)2 SCBj . 7C-C5 H5 Fe- (C0)2 C ^ , and 7C-C5 H5 Fe(C0)2 S0 2 CH3 ...... 124 10. Infrared CO Stretching Frequencies of ti—Cj Hj Fe(CO)2 R Complexes .................. 126 11. Proton Magnetic Resonance Spectra of 7t-C5 Hj Mo ( CO )3 R ............................. 136 12:. Some Physical Properties of Mercury S u l f o n y l s ................................... 142 13. Proton Magnetic Resonance Spectra of Mercury Derivatives, RHgR' ............... 144 v TABLES, CONTD. Table Page 14. A Comparison of the Infrared Absorption Frequencies of C6 Hg HgS02 C6 H5 and C6 H5 HgSC6 H , ................................. 155 15. Infrared SO Stretching Frequencies of RHgS02R ..................................... 156 16. Infrared Absorption Frequencies of Iron-Tin Complexes ....................... 158 17. Infrared Absorption Frequencies for Compounds Prepared from NaMn(CO)5 and RS02 C l ................................. 162 18. Some Physical Properties of the Acetyl Derivatives of C5 H5 Fe(CO)2 CH3 .... 174 19. Proton Magnetic Resonance Spectra of 7C-C5 H5 Fe(CO)(COCH3 )PR3 ....................176 20. Infrared CO Stretching Frequencies of tc-C5 H5 Fe ( CO ) ( COCB3 ) PR3 C omplexe s ............ 177 FIGURES Figure Page 1. Similarity of Carbon Monoxide, Sulfur Dioxide and Their Compounds ........ 18 2. Apparatus for the Preparation of [ic-C5 Hj Fe(CO)j[] 2 and [te-Cj Hj MoCCO)£] 2 .... 29 3. Apparatus for Drying and Condensing S02 . 35 4. W Irradiation Apparatus .............. 38 5. Possible Structures of Tt-C5 H5 Fe(CO)2 S02 CE^ R . 114 6 . A Comparison of the MUR Spectra of C5 H5 Fe(CO)2 CI^ Cg H5 and CjHsFeCCO^- S02 CHa C6 % 118 7. A Comparison of the Infrared Spectra of C5 H5 Fe(CO)2 CH5 and C5 % Fe.(CO)2 - S0 2 CH3 ..................................... 123 8 . Proton Magnetic Resonance Spectra of the Methyl Protons in C2 H5 HgS02 C2 H5 ...... 149 9. A Comparison of the Infrared Spectra of Cg H5 HgSCg H5 and C6 H5 HgS02 C6 H5 ............ 154 vii INTRODUCTION The chemical literature of the last ten years contains a rapidly increasing number of examples of the so-called insertion reaction in organometallic chemistry. Although some aspects of the insertion reaction are not yet under­ stood, it has already become an extremely useful tool in chemical syntheses. Insertion, as Heck (1) notes in a recent review, is generally described as the addition of a covalent metal compound, M-Z, to a neutral unsaturated molecule, :Y, to form a new complex where :Y is ultimately bonded to both the metal and the atom which was initially attached to the me tal. M-Z + sY ------- > M-Y-Z (1) Equation (1> is the simplest representation of the insertion reaction. It does not consider the role of sol­ vent, if any, in the mechanism, the nature of M-Z, or the nature of the final product, M-Y-Z. Nevertheless, it is relatively good representation of some of the less compli­ cated insertion reactions because insertion may be des­ cribed as merely a special case of an addition reaction involving a covalent metal compound. The molecule :Y may be carbon monoxide, an acetylene, an olefin, a carbon-nitrogen compound, a conjugated diene, a carbene, or several other unsaturated compounds. Cova­ lent metal compounds which are known to undergo insertion contain a reactive metal-hydrogen, metal-metal, metal- carbon, metal-oxygen, metal-nitrogen, or metal-halogen linkage. Of particular interest in this investigation are those reactions involving insertion into a metal-carbon bond. The first example of such an insertion reaction was reported by Coffield and co-workers in 1957 o They found that methylmanganese pentacarbonyl reversibly absorbs carbon monoxide to form acetylmanganese pentacarbonyl. (2 ) Ethyl- and phenylmanganese pentacarbonyl react with carbon monoxide in the same manner. Further investigation on the methyl derivative (3) using C14-labeled CO showed that a carbon monoxide already coordinated to the manganese is being inserted rather than the incoming carbon monoxide. CHj Mn(CO)5 +C*0 ---- } (CH3 C0)Mn(C*0)5 (2) The alkylcobalt tetracarbonyls react analogously with carbon monoxide, forming acylcobalt tetracarbonyls. (4) Like that of the corresponding manganese compounds, the reaction is reversible. (5 ) HCo(CO),, +G0 (200)00(00),, (3) The cobalt complexes are much more reactive than the man­ ganese compounds, however, and must be studied below -35°Ge (6 ) Acetylcobalt tetracarbonyl dissociates about 2 2 5 0 times faster than acetylmanganese pentacarbonyl at 25°C., the difference between the solvents, ether and the diethyl ether of diethylene glycol, being neglected. (5 ) Consequently, much more is known about the manganese system. Insertion of carbon monoxide takes place with many other transition metal alkyl and aryl complexes. The methyl derivative of cyclopentadienyliron dicarbonyl will add to CO to give the acetyl compound. (2) m-C5 H5 5*6 (0 0 ) 2 CH, +00 --- > m-C5 ^ Fe(C0)2 (C0CH3 ) (4) Unlike the acyl derivatives of manganese and cobalt, acyl- iron complexes completely decompose on heating rather than undergo decarbonylation to form the alkyl derivatives. (2 ) king has recently been able to convert a large variety of these acyl complexes of iron to alkyls or aryls with the use of ultraviolet light. (7 ) ir-C5 H5 5'e(CO)2 (C0C6 K; ) — 7t-C5 H5 Fe(C0)2 C6 Hg +00 (5) Interestingly enough, although hydrogen-containing alkyl and aryl cyclopentadienyliron dicarbonyls readily and reversibly insert carbon monoxide, there is no evidence that the corresponding perfluoroalkyl and -aryl derivatives will do so. There are many examples of the decarbonylation of perfluoroacyl derivatives of other metal ions. (7 * 8 , 9, 10) Some perfluroacylcobalt tetracarbonyl compounds have been obtained (8 , 9
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