Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1983 NMR studies of phosphorus ligand complexes of silver and cobalt Steven Mark Socol Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Socol, Steven Mark, "NMR studies of phosphorus ligand complexes of silver and cobalt " (1983). Retrospective Theses and Dissertations. 8962. https://lib.dr.iastate.edu/rtd/8962 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. UniversiW Microrilms International 300 N. Zeeb Road Ann Arbor, Ml 48106 8407126 Socol, Steven Mark NMR STUDIES OF PHOSPHORUS LIGAND COMPLEXES OF SILVER AND COBALT Iowa State University PH.D. 1983 University Microfilms Intsrncitions! 300 N. zeeb Road, Ann Arbor, Ml48106 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 NMR studies of phosphorus ligand complexes of silver and cobalt Steven Mark Socol A Dissertation Submitted to the 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. For the Major Departln^ Signature was redacted for privacy. For ollege Iowa State University Ames, Iowa 1983 il TABLE OF CONTENTS Page PREFACE 1 PART I. COORDINATION OF PHOSPHORUS LIGANDS TO SILVER(I) 4 INTRODUCTION 5 EXPERIMENTAL 15 Procedures 15 Materials 15 Preparation of Compounds 16 X-ray Data for [Ag(P(NMe2)3)2]BPh4 24 RESULTS AND DISCUSSION 27 Cationic Phosphorus Ligand Complexes of Silver(I) 27 Neutral Complexes of Silver(I) Complexed to Phosphorus Ligands 44 Ligand Competition Experiments 50 X-ray Structure of CAg(P(NMe2)3)2]BPh4 53 PART II. NMR STUDIES OF PHOSPHORUS LIGAND COMPLEXES OF COBALT 61 INTRODUCTION 62 EXPERIMENTAL 68 Procedures 68 Materials 69 Preparation of Compounds 69 Preparation of [Co(P^)g]^'*' and [Co(2)5]^ Complexes by Disproportionation of Co(II) 79 iii RESULTS AND DISCUSSION • 82 Preparation of Phosphorus Ligand Complexes of Cobalt(III) 82 Steric and Electronic Influences in the Disproportionation of Co(II) by Phosphorus Ligands 83 Catalytic Transesterification of Monocyclic Phosphite Esters During the Disproportionation of Co(II) 94 S^Co NMR Studies of Ligand Field and Ligand Conformations in [Co(P)g]J+ Complexes 104 Relaxation Effects in Octahedral Cobalt(III) Complexes 122 PART III. CRYSTAL AND MOLECULAR STRUCTURE OF P(0-2,6-C6H3Me2)3 140 INTRODUCTION 141 EXPERIMENTAL 142 RESULTS AND DISCUSSION 145 REFERENCES 151 ACKNOWLEDGEMENTS 161 APPENDIX: FINAL POSITIONAL AND THERMAL PARAMETERS FOR [Ag(P(NMe2)3)2]BPh4 AND P(0-2,6-C6H3Me2)3 163 iv LIST OF TABLES Page Table 1. Phosphorus compounds discussed in this dissertation 2 Table 2. NMR properties of nuclei 10 Table 3. Ligand cone angles, sum of ligand substituent contributions to v(C0)(A,) in NifCOjgL, coupling of corresponding ligand selenides and maximum value of n in [AgLp] 29 Table 4. ^^P NMR chemical shifts and silver(107)-phosphorus{31) couplings as a function of L and n in [AgL^l^X" complexes 31 Table 5. Melting point and conductance data for isolated ionic silver complexes 34 Table 6. Comparison of solution and solid state ^^P NMR for CAg(7_)2]BPh4 and Ag(24)BFA 40 Table 7. ^^P NMR chemical shifts as a function of coordination number n in complexes of d^" metals 42 Table 8. ^^P NMR, melting point, conductivity and molecular weight data of non or slightly conducting silver complexes 47 Table 9. Conductivity of AgLgNOg complexes as a function of the cone angle of L 50 Table 10. Interatomic distances and selected intramolecular contacts (A) and their estimated standard deviations (in parentheses) for [Ag(P(NMe2)3)2]BPh4 56 Table 11. Bond angles (deg) and their standard deviations (in parentheses) for [Ag(P(NMe2)3)2]BPh4 57 Table 12. Phosphorus-nitrogen bond distances (A) and sum of the angles around nitrogen (deg) in CAg(^)2]BPh4 58 Table 13. Boiling points and ^^P NMR chemical shifts of 2-substituted-l,3,2-dioxaphospholanes 70 Table 14. NMR chemical shifts of selenophosphates 78 Table 15. ^^C NMR chemical shifts and 13c_31p coupling constants (in parentheses) of 2-methoxy-l,3,2-dioxaphosphorinanes, their [CoLg] complexes and some sulfide derivatives 88 V Table 16. NMR chemical shifts and coupling constants (in parentheses) of 1,3,2-dioxaphospholanes, their cobalt complexes and some sulfide derivatives 96 Table 17. Spectroscopic data for [CotP)^]^* complexes and ^JSeP of selenated ligands 107 Table 18. Configurational equilibrium data for [Co(39)fi3^"'" and [Co(^)6r+ —^ 109 Table 19. CO stretching frequencies in M(C0)4(P)2 complexes 118 Table 20. ^^Co NMR chemical shifts of [Co(17)y(9)g_v](BF4)3 119 Table 21. NMR properties of ®^Cu and ®^Cu nuclei 124 Table 22. Ti of ^%o in [Co(P)g]3^ complexes and ^%o NMR linewidths 126 Table 23. ^^P NMR data for [CofPjg]^* complexes 128 Table 24. Phosphorus-cobalt coupling constants 135 Table 25. One-bond couplings to phosphorus in some acyclic and bicyclic phosphite ester systems 136 Table 26. T^ and T2 values of ^^P in [C6(P)g]3+ compounds 138 Table 27. Interatomic distances (A) and their standard deviations (in parentheses) for 24 143 Table 28. Bond angles (deg) and their standard deviations (in parentheses) for_24 144 Table 29. Least squares planes for ^ 147 Table 30. Structural data for phosphite esters 148 Table Al. Final positional parameters and their estimated standard deviations (in parentheses) for [Ag(P(NMe2)3)2]BPh4 164 Table A2. Thermal parameters and their estimated standard deviations (in parentheses) for CAg(P(NMe2)3)2]BPh4 167 Table A3. Final positional and thermal parameters and their estimated standard deviations (in parentheses) for P(0-2,6-C6H3Me2)3 169 vi LIST OF FIGURES Page Figure 1. The phosphorus ligand cone angle as defined by Tolman 8 Figure 2. Some possible conformations of tri s(di alkylamino)phosphi nes 13 Figure 3. NMR spectrum of [Ag(19)a]I at -88°C in 75/25 CH2Cl2/dg-acetpne. JheTg-P coupling constants refer to the ^"'Ag nucleus 45 Figure 4. ORTEP drawing of [Ag(2)2]^ cation 54 Figure 5. ORTEP drawing of [Ag(7_)2]BPh4 55 Figure 6. 2-Alkoxy-l,3,2-dioxaphospholanes 85 Figure 7. Possible mechanism of transesterification of 2^ upon reaction with Co(II) by equation 12 100 Figure 8. Series of pseudorotations which isomerize a coordinated 1,3,2-dioxaphosphorinane 101b Figure 9. Possible rotameric configuration of a [CoLg]^"^ ion where L is a monocyclic phosphite ester. P atoms coordinated to Co are not shown 110 Figure 10.