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Reactions of Sulphure Dioxide with Transition Metal Unsaturated

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Reactions of Sulphure Dioxide with Transition Metal Unsaturated 70-26,354 ROSS, Dominick Allan, 1940- REACTIONS OF SULFUR DIOXIDE WITH TRANSITION METAL UNSATURATED HYDROCARBON COMPLEXES. The Ohio State University, Ph.D., 1970 Chemistry, inorganic University Microfilms, A XEROX Company, Ann Arbor, Michigan REACTIONS OF SULFUR DIOXIDE WITH TRANSITION METAL ♦ UNSATURATED HYDROCARBON 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 Dominick Allan Ross, B.S. ****** The Ohio State University 1970 Approved by Department of Chemistry ACMOWLEDGMENTS Much credit for the completion of this dissertation must be given to my wife, Sharon. Without her constant encouragement, the task would have been much more difficult. I would like to thank Dr. Andrew Wojcicki for his helpful guidance during the course of this research. Finally, I am indebted to the National Science Foundation and the Petroleum Research Fund, administered by the American Chemical Society, for financial support. VITA November 16, 1940 Born - Binghamton, New York 1964 ..... B.S., The Ohio State University, Columbus, Ohio 1964-1966 .... Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1966-1969 ...... Research Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio FIELDS OF STUDY Major Field: Inorganic Chemistry. Dr. Andrew A. Wojcicki iii CONTENTS Page ACKNOWLEDGMENTS o»*oe»ft0to»««o«»aODfte»»ee0eaooae«e«««o»e««oeee» XX VITA oo.ooooo.eooao..........ooo.oottoooooo......e.«oo..o.....oo XXX TABLES . o o . o • o . o o o o . o o • a . o •o • « o ..o o..•••« o...» VX FIGURES ................. viii INTRODUCTION I EXPERIMENTAL saaaoaoaoasa.e.aaoo.aee.ees.se.oeooa.eooaaa.oeaeoo X6 St^rtXH^ 6rxclls eaaaeoeaeaaaaae.eaeeaao.ae.oooaeeee.oaeeoe X6 General Remarks on the Preparation of Allylic Sulfinato Complexes............ ........... 26 Preparation of Allylic Sulfinate Complexes of Cyclopentadienyliron Dicarbonyl ........................... 28 Preparation of Allylic Sulfinate Complexes of Cyclopentadienylmolybdenum Dicarbonyl ..................... 38 Reactions of Cyclopentadienylmetal Dicarbonyl Complexes wxth Sulfur Dxoxxde o............................ 43 Reactions of Boron Trifluoride with Sulfinate Complexes of Cyclopentadienyliron Monocarbonyl ........a... 51 RESULTS AND DISCUSSION ............••....•..•.•».«.o.eo..o...«o 5^ Investigation of Allylic Sulfinato Complexes ...... 56 Preparatxon of the Complexes ...o............................ 58 Physical Properties of Sulfinates .... 61 Infrared Studies .............. 6l Proton Magnetxc Resonance Studxes ............«...«.......... 67 Dxscussion of Mechanxsms .......o . « . o . 113 Reactions of Cyclopentadienylmetal Dicarbonyl Complexes wxth Sulfur Dxoxxde ............................. 120 Reactions of Boron Trifluoride with tr-C_HcFe(C0)„PR,.S(0)oCH , ................................ 132 5 5 2 3 2 3 SUMMARY ............. a........... 142 APPENDIX A .......o.ooooo.............o.«o«.«.*o....«*..e«....ol46 APPENDIX B .................. 152 iv CONTENTS'(Coatd.) Page APPENDIX C »C»000900®«000«#» 1^8 BIBLIOGRAPHY................................................ 163 v TABLES Table Page 1® Infrared S-0 Stretching Frequencies of Compounds Containing ^SOp— ooo............0.09.0.0.00.00 ^ 2. Infrared S-0 Stretching Frequencies of Substituted Sulfinatocarbonyl Complexes .... 6 3® SO^ Insertion Products of Allylic, Propargylic, and AlleniC Compounds .••o.».eooo.oeoooo..«eooo.oo.oooo® 10 4. Analytical and Molecular Weight Data for Allylic SulfmatO Complexes of Iron oooo.oooo.oo.ooob.ooo.ooo.o. 37 5® Analytical and Molecular Weight Data for Allylic Sulfinato Complexes of Molybdenum....... 44 So S-0 Stretching Frequencies of Allylic Sulfinato Complexes .. oo.' o • ® «•...»«. ®...«... ®. o. o. o o... Sb 7® C-0 Stretching Frequencies of Allylic Sulfinato Complexes o®®...®..®®.®.®..................... SS 8. Proton Magnetic Resonance Spectra of Allylic -CH-.C-H> Fe(CO)_R and 7^CH,CcH,1Fe(C0)oS0_R Complexes ............... ?..?.............. 85 9® Proton Magnetic Resonance Spectra of Allylic rr-l,3-(C.Hc)„Cc.H,Fe(C0)_R and /r-l,3-(C.HJ_C_fL,Fe(C0)o- S02R Complexes ............... 89 10® Proton Magnetic Resonance Spectra of Allylic ?f'-(CH_)t-Cc.Fe(CO)_R and 7T-(CH,)[.C_Fe(C0)DS0-R Complexes .............. ?..?...... 96 11. Proton Magnetic Resonance Spectra of Allylic 7T-C H.-MoCCO) P(0C,H,_)xR and /^■Ct-H[-Mo(C0)_P(0CAHt.)xS0-R Complexes ........ ?.?......77... 112 12. Isomeric Distribution of Sulfinates from SO^ Insertion of Allylic Complexes of Iron ..... 117 13® Isomeric Distribution, of Sulfinates from S02 Insertion of Allylic Complexes of Molybdenum......... 119 vi TABLES (Contd.) Table Page 1 * • 14. Proton Magnetic Resonance Spectra of Propargylic lf-C_H_Fe(CO)aR and 7f-C,-HI_Fe(C0 )o(S0 ,C,H_)..... ;...... 124 5 5 2 5 5 2245 15« B-F Stretching Frequencies of 1:1 Boron Trifluoride Complexes ............................ 135 16. Infrared Spectra of tf’-C^H^FeCCO)P(n-ClfHg JjSC OjgCH-j and ^-C^5Fe(C0)P(n-CI|H9)3S(0)2CH3.BF3................ 136 17. Infrared Spectra of ^-CcHcFeCCOMcgHc^sCOjpCH, and >r-C5H5Fe(C0 )P(C6H p 3S(0 )2CH3 .BF^ ............ 137 vii FIGUHES Figure 1. Ultraviolet irradiation apparatus ........... 2. Pressure reaction vessel. ........... 3. A comparison of the pmr spectra of: A. fl’-CH3C5H*iFe(C0)2CH2CH=C(CH3)H; B. ■rf-CH3C5Hi|.Fe(C0)2S02C(CH;5)HCH=CH ..... 4. A comparison of the pmr spectra of: A. CICH2CH=C(CH3 )H;. B. TT-CjK^Fe (C 0) 2CH2CH=C ( CH3 )H; C. 7r-C^H^Fe ( CO ) 2S02C (CH3 )HCH=CH ...... 5® A comparison of the pmr spectra of: A. »r-CH3C5H/fFe(C0)2CH2CH=C(CH3)2; B. A mixture containing 73% fr-CH3C5H/fFe(C0)2S02CH2CH=C(CH3)2 and Z3% »’-CH3C3H/tFe(C0)2S02C(CH3)2CH=GH2........ 6 . A comparison of the pmr spectra of: A. 7r_c5H5Fe(C0)2S02CH2CH=C(CH3)2; B. A mixture containing 76% 1T-C cHcFe ( CO ) 2S02CH2CH=C (CH3 ) 2 and Zb% «r-C3H5Fe(C0 )2SG2C( CH3 )2CH=CH2; C. A mixture containing 6% ^-C5H5Fe(CO)2S02CH2GH=C(CH3 )2 and 9k% ^•-C5H5Fe(C0)2S02C(CH3)2CH=CH2 .......... 7® A comparison of the pmr spectra of: A. ^•CH3C5HzfFe(C0)2CH2CH=C(C6H3)H; B. A mixture containing 83% Tr-CRjPcfiifie(CO)2S02CH2CH=C(CgHc )H and 13% 7r-CH3C3H2jFe(C0)2S02C(C6H5)HCH=CH2 8m A comparison of the pmr spectra of: A. /r-C5H5Fe(CO)2S02CH2CH=C(C6H5 )H; B. A mixture containing 80% »r-C5H5Fe(CO)2S02CH2CH=C(C6H5 )H and 20# if-CjHjFe ( CO ) 2S02C (C5H5 )HCH=CH2; C. A mixture containing 30$ IT-C3H3Fe(CO)2S02CH2CH=C(C6H5 )H and 70% 7f~C^H^Fe( CO ) 2S02C ( C6H5 )HCH=CH2 .......... FIGURES (Contd.) Figure ' Page 9. A comparison of the pmr spectra of: A. ^-l,3-(C6H5 )2C5H3Fe(C0)2CH2CH=C(CH3)25 Bo A mixture containing 75% ,3-( C5H5 )2CcH3Fe (CO)2S02CH2CH =C( CH3 )2 and 2 % ^•-1,3-(C5H5 )2C5H3Fe(CO)2S02C(CH3 )2CH=CH2 .... 87 10. A comparison of the pmr spectra of: A. 77--( CH3 ) cCcFe ( CO ) 2CH2CH=C ( CH3 )H; B. rr- ( CH3 )^C3F e ( CO ) 2S02C (CH3 )HcH=CH ................. 90 11. A comparison of the pmr spectra of: A. rr- ( CH3 ) 5C3F e ( CO) 2CH2CH=C ( CH3 ) 2; B. >7"- ( CH3 ) 3C3Fe ( CO ) 2S 02CH2CH=C (CH3 ) 2; C. A mixture containing 60& 7r-(CH3 )5C5Fe(C0 )2S02CH2CH=C(CH3)2 and k0% 7f-(CH3 )5C3Fe(C0)2S02C(CH3 )2CH=CH2 ............ 92 12. A comparison of the pmr spectra of: A. /T-(CH3 )cC3Fe(CO)2CH2CH=C(CgHc )H; B. 7f- ( CH3 ) 5C3F e ( CO ) 2S02CH2CH =C (Cglhj )H ......... 9** 13. The isomers of a Tr-C^Hi-MoCCO^LR complex ..... 99 14. A comparison of the pmr spectra of: A. ( CO ) 2P( OC6H5 )3CH2CH=C (CH3 )H; B. A mixture containing 80& jt'-CcHcMoCC0)2P(OCgHc)3S02CH2CH=C(CH3 )H and 20# n'-C3H3Mo(C0)2P(0C6H3)3S02C(CH3)HCH=GH2............ 102 13. A comparison of the pmr spectra of: A. jr-CcH5Mo(C0)3CH2CH=C(CH3)H; B. jr-^^MoC CO^SO^C CH3 )HCH=CH .................... 10*f 16. A comparison of the pmr spectra of: A. JJS-C^HcMoC C0)2P( OCgHc )3CH2CH=C( CH3)2; B. »*-C3H5Mo(C0)2p(0CgH5)3S02CH2CH=ClCH3)2 ........... 108 17. A comparison of the pmr spectra of: A. /r-C^H^MoC C0)2P( OG6H5 )3CH2CH=C ( C6H5 )H; B. Tr-C^no(C0)2P(0C^E5)^S02Cli2p E = C ( G ^ ) H .......... 110 18 . A comparison of the pmr spectra of: A. tT-GcHcF e ( CO ) 2CH2CsCCH3 ; B. Tf-C^H^FeCC0)2(SO^ijH^ .......... 122 ix FIGURES (Contd.) . Figure * Page 19. Infrared spectrum of Jf-C^H^FeCCO)P(n-Cz^Hg)3S02CH-z .BF-z in the regions 3500-1300 and 1300-^+50 c m ~ l ............ 138 20. Infrared spectrum of 7T-CcHcjFe(CO)£ -C=C(CH*)S(0)OCH2 ) in the regions 3500-1300 and 1300-300 c m ~ l ...... 154 x INTRODUCTION Insertion reactions in organometallic chemistry have been studied extensively in the last ten years® They are important because: (l) Their use often provides facile synthesis for organometallic compounds not accesible by alternative routes® (2) In identifying their role, many important processes, particularly catalytic processes, are better understood® Lappert and Prokai (1) have recently reviewed insertion reactions of metal (M) complexes of the type X^M-R according to the nature of the inserting group® In general, they can be classified as 1,2-addition to an unsaturated substrate, 1,1-addition to an unsaturated substrate, and oxidative 1,1-addition to low coordination number compounds, tran­ sient species, or atoms® Examples of each class of reaction are given by equations (1), (2), and (3), respectively (2, 3» **»)• + (1) + 8 (2) (C0H_),Si-H + :CC1_ » (C_H)SiCClH (3) O > *■ 2 3 3 1 Of particular interest to this investigation are insertion re­ actions of sulfur dioxide with complexes containing metal-carbon bonds® Oxidative 1,1-addition reactions are not considered further since they
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