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Synthetic, Sterochemical, and Electronic Studies of Organophosphorous Ligands and Their Transition Metal Complexes James Timothy Spencer Iowa State University

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Synthetic, Sterochemical, and Electronic Studies of Organophosphorous Ligands and Their Transition Metal Complexes James Timothy Spencer Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1984 Synthetic, sterochemical, and electronic studies of organophosphorous ligands and their transition metal complexes James Timothy Spencer Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Spencer, James Timothy, "Synthetic, sterochemical, and electronic studies of organophosphorous ligands and their transition metal complexes " (1984). Retrospective Theses and Dissertations. 7727. https://lib.dr.iastate.edu/rtd/7727 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. 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. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed. For blurred pages, a good image of the page can be found in the adjacent frame. If copyrighted materials were deleted, a target note will appear listing the pages in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photographed, a definite method of "sectioning" the material has been followed. It is customary to begin filming at the upper left hand comer of a large sheet and to continue from left to right in equal sections with small overlaps. If necessary, sectioning is continued again—beginning below the first row and continuing on until complete. 4. For illustrations that cannot be satisfactorily reproduced by xerographic means, photographic prints can be purchased at additional cost and inserted into your xerographic copy. 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. UniversiV Microfilms International SOON.Zeeb Road Ann Arbor, MM8106 8423673 Spencer, James Timothy SYNTHETIC, STEREOCHEMICAL, AND ELECTRONIC STUDIES OF ORGANOPHOSPHORUS LIGANDS AND THEIR TRANSITION METAL COMPLEXES Iowa State University PH.D. 1984 University Microfilms Intorn&tioris! 300 N. Zeeb Road, Ann Arbor, Ml 48106 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. Glossy photographs or pages 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 International Synthetic, stereochemical, and electronic studies of organophosphorus ligands and their transition metal complexes James Timothy Spencer A Dissertation Submitted to thé Graduate Faculty in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Department: Chemistry Major: Inorganic Chemistry Approved: Signature was redacted for privacy. Signature was redacted for privacy. 'r ^e mjoT" )ep<ô#^wi^ Signature was redacted for privacy. For theSrariuate College Iowa State University Ames, Iowa 1984 ii TABLE OF CONTENTS Page LIST OF COMPOUNDS xvii LIST OF ABBREVIATIONS xxvi DEDICATION xxvii PREFACE 1 PART I. PREPARATION, STRUCTURE, AND TRANSITION METAL COMPLEXES OF DIOXAPHOSPHORUS LIGANDS 3 INTRODUCTION 4 EXPERIMENTAL 29 Materials 29 Techniques 30 Preparations 35 Reactions 62 RESULTS AND DISCUSSION 68 Reactions of ^P-X Compounds with X Acceptors 68 Reactions of ^P(X)-Transition Metal Complexes with X Acceptors 73 Reactions of ^P(NR2) Compounds with Acids 74 Reactions of %ZP(NR2)-Transition Metal Complexes with Acids 85 Reactions of %)P-C1 Compounds with Transition Metal Nucleophiles 90 Dimeric Iron Complexes 92 PART II. CRYSTALLOGRAPHIC STUDIES OF THE CIS AND TRANS 171 COMPLEXES OF [Fe(T,5-Cp) (CO) (y-5,5-Diniethyl-1,3,2- di oxaphosphori nane) INTRODUCTION 172 i1i EXPERIMENTAL 174 Structural Determination of the cis-[Fen®-Cp)(C0)(u-5,5-DMP)]2 174 Structural Determination of the trans-CFe(n®-Cp)(CO){u-5,5-DMP)]2 177 RESULTS AND DISCUSSION 222 PART III. CRYSTALLOGRAPHIC STUDY OF [Fefn^-C Hg)(CO)(w. 251 4,4,5,5-tetramethyl -l,-3,2-dioxaphospr?olane)2Fe(C0)3] INTRODUCTION 252 EXPERIMENTAL Synthesis of [Fefn^-CgHgiiCOjtw-PfOCfMejgCtMelzOjjgFefCO)]] 264 Structural Determination 265 RESULTS AND DISCUSSION 284 PART IV. STEREOCHEMICAL STUDIES OF ORGANOPHOSPHORUS TRIESTERS WITH PHOSPHORUS AS THE PRIMARY CHIRAL SITE 300 INTRODUCTION 301 EXPERIMENTAL 311 Materials 311 Techniques 311 Preparations 314 RESULTS AND DISCUSSION 336 Chiral Triesters 336 Diastereomeric Organophosphorus Esters 346 Chiral Stationary Phase HPLC 355 Diastereomeric Platinum(II) Complexes 357 CONCLUSIONS 366 REFERENCES ' 369 ACKNOWLEDGMENTS 383 APPENDIX I 385 Stereopair Drawings and Unit Cell Drawing of cis-[Fe(n^-Cp) (CO)- (ii-5,5-dimethyl -l,3,2-dioxaphosphor1narie) APPENDIX II Stereopair Drawings and Unit Cell Drawings of trans-[Fetn^- Cp)(C0)(u-5,5-diniethy1-l,3,2-dioxaphosphorinane)]2 APPENDIX III r , , „ Stereopair Drawings and Unit Cell Drawing of LFe(n^-CgHg)(CO)()j 4,4,5,5-tetramethyl-l,3,2-dioxaphosphol300)2^0(00)3] LIST OF TABLES Table 1. 12 NMR data for free phosphenium ions Table 2. 23 NMR data for phosphenium ion-transition metal complexes Table 3. 25 Infrared data for phosphenium ion and precursor iron carbonyl complexes Table 4. 60 Rf values for CFe(n®-Cp)(C0)L]2 complexes on alumina Table 5. 73 ^^P NMR data for the reactions of M(CO)r(Cl-P^ ) (M = Cr, W) with AlClg Table 6, 74 Aminophosphorus(III) compounds reacted with HSOoCFo by Dahl Table 7. 75 NMR chemical shifts and coupling constants data for Me2N-P systems Table 8. 77 ^^P NMR data for Me2N-PC + HB reactions Table 9. 82 Conductance data for (Me2N)PX2 + HSOgCFg and standard systems Table 10. 1 \/ 86 NMR data for MegiN-P-MtCO)^.systems Table 11, 87 31p NMR data for M(C0)^(Me2N-PC ) + HB reactions Table 12. 88 ^^P NMR data for the FefCOj^fS) + HSO3CF3 system Table 13. 89 ^^P NMR data of the intermediates from the M(00)^^(8^) + HB system VI Table 14. 90 Selected metal nucleophiles and rate constants for alkylation Table 15. 99 Mass spectral data for 26 and cis and trans-CFefqS- Cp)(C0)(p-5,5-DMP)]2 Table 16. 104 NMR data for precursor chlorophosphorus compounds Table 17. 117 NMR data for [Fe(n®-Cp)(C0)(L)]2 systems Table 18. 142 NMR data for precursor chlorophosphorus(III) compounds Table 19. 145 NMR data for [FeCn^-Cp)(C0){L)]2 systems Table 20. 148 NMR data for [Fe(nS-Cp)(C0)(L)]g systems Table 21. 161 Infrared data for [Fe(n^-Cp)(C0)(L)]2 systems Table 22. 175 Experimental crystallographic data for cis-[Fe(n5- CP)(C0)(M-5,5-DMP)]2 Table 23. 178 Fractional atom coordinates for cis- [Fe{n^-Cp)(C0)(u-5,5-DMP)]2 with estimated standard deviations Table 24. 179 Hydrogen fractional coordinates for cis-[Fe(n5-Cp)- (C0)(y-5.5-DMP)]2 Table 25. 180 Anisotropic thermal parameters for cis- [Fe(n5-Cp)(C0)(u-5,5-DMP)]2 Table 26. 182 Structure factor tables for cis-[Fe(n5-Cp)(CO)(u- 5,5-DMP)]2 vii Table 27. 198 Experimental crystal!ographic data for trans- [Fe(n5-Cp)(C0){M-5,5-DMP)\ Table 28. 200 Fractional atom coordinates for trans-[Fe{n®-Cp)(CO)(ji- 5,5-DMP)]2 with estimated standard deviations Table 29. 202 Hydrogen fractional coordinates for trans-[Fe(n5- Cp)(C0)(u-5,5-DMP)]2 Table 30. 204 Anisotropic thermal parameters for trans-[Fe(n5- CP)(C0){M-5.5-DMP)]2 Table 31. 206 Structure factor tables for trans-[Fe(n5-Cp)(CO)- (y-5,5-DMP)^2 Table 32. 223 Bond distances (A°) in cis-[Fe{n5-Cp)(C0)(y-5,5- DMP)]2 with estimated standard deviations Table 33. 224 Selected non-bonded distances (A°) in cis-[Fe(n5- Cp)(C0)(u-5.5-DMP)]2 Table 34. 225 Bond angles (degrees) in cis-[Fe(n5-Cp)(C0)(n-5,5- DMP)]2 Table 35. 226 Least-squares planes in cis-[Fe(%5-Cp)(C0)(p-5,5- 0MP)]2 Table 36. 227 Dihedral angles between planes (degrees) in cis- CFe(Ti5-Cp) (CO) (p-5,5-DMP)]2 Table 37. 228 Bond distances (A°) in trans-[Fe(n5-Cp)(C0)(y-5,5- DMP)]2 with estimated standard deviations Table 38.
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