Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1983 Structural and electronic influences on phosphite basicity and its application to heterogeneous and homogeneous catalysis David Evan Schiff Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Schiff, David Evan, "Structural and electronic influences on phosphite basicity and its application to heterogeneous and homogeneous catalysis " (1983). Retrospective Theses and Dissertations. 8960. https://lib.dr.iastate.edu/rtd/8960 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. 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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. University Microfilms international 300 N. 2eeb Road Ann Arbor, Ml 48106 8407124 Schiff, David Evan STRUCTURAL AND ELECTRONIC INFLUENCES ON PHOSPHITE BASICITY AND ITS APPLICATION TO HETEROGENEOUS AND HOMOGENEOUS CATALYSIS Iowa State University PH.D. 1983 University Microfilms Intornâtionâ! SOO 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 structural and electronic influences on phosphite basicity and its application to heterogeneous and homogeneous catalysis by David Evan Schiff 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. Charge of Major Work Signature was redacted for privacy. FÔ^r the Major DepartgiMt Signature was redacted for privacy. For the Gradu Iowa State University Ames, Iowa 1983 ii TABLE OF CONTENTS Page PREFACE 1 PART 1. THE CATALYTIC PROPERTIES OF HOMOGENEOUS AND HETEROGENEOUS NiL^ (L = PHOSPHITE) COMPLEXES 12 INTRODUCTION 13 Hydrocyanation of olefins 38 Unanswered questions in Gultneh's work 42 Heterogenized homogeneous catalysts 47 EXPERIMENTAL PROCEDURES 56 Preparations 60 Results and discussion 78 Use of Lewis acid cocatalysts in the isomerization 91 of 3-butenenitrile Crystal and molecular structure of Ni(6)4 102 Effect of substitution of oxygens in tTTe phosphorinane ring by carbon 112 Asymmetric isomerization of (CH3CH2)(CH3)C=CHCH2CN 135 Hydrocyanation of 1,3-butadiene to adiponitrile 136 Heterogenized NiL^ catalysts 141 PART II. STEREOELECTRONIC EFFECTS OF CYCLIZATION IN AMINO- PHOSPHINE SYSTEMS: A STRUCTURAL, PES, AND NMR STUDY OF Me2NP(0CH2)2CMe2 AND CH2(CH2CH2)2NP(0CH2)2CMe2 153 INTRODUCTION 154 Experimental procedures 157 Preparations 159 Experimental details for X-ray data collection for compounds ^ and ^ 162 Results and discussion 164 1i i PART III. THE USE OF PHOSPHORUS CONTAINING DERIVATIZING REAGENTS FOR THE ANALYSIS OF ALCOHOLS 188 INTRODUCTION 189 EXPERIMENTAL PROCEDURES 194 Results and discussion 196 CONCLUSIONS 203 REFERENCES 205 ACKNOWLEDGMENTS 215 APPENDIX 1. STRUCTURE FACTORS FOR Ni(6)^ 216 APPENDIX 2. STRUCTURE FACTORS FOR 30 222 APPENDIX 3. STRUCTURE FACTORS F0R'_M 227 APPENDIX 4. STRUCTURE FACTORS FOR 21 232 IV LIST OF TABLES Table 1. 2 Compounds described in this thesis Table 2. 20 Various ligand cone angles for some selected phosphorus ligands Table 3. 29 Rates of catalytic isomerization of 3-butenenitrile by NiL^/acid (1/10) systems in benzene at 25°C as a function of the size of the exocyclic phosphorus substituent Table 4. 46 Rates of isomerization of 3-butenenitrile by NiL^/FgCCOOH systems in benzene at 25°C Table 5. 48 Relative advantages and disadvantages of different types of catalysts Table 6. 61 Ranges of chemical shift (rel. to H3PO4) for compounds discussed in this thesis Table 7. 80 NMR chemical shifts and Jp_|^ values of some selected monocyclic phosphite ligands upon protonation with FSO-H at -50°C ^ Table 8. 83 31p_77se spin-spin couplings and NMR chemical shifts (rel. to H3PO4) of some selected selenophosphoryl compounds. Table 9. 92 Comparison of activity of Lewis acids to H"*" as a cocataly'st in the-isomerization of 3-butenenitrile. V Table 10. 97 NMR data for various AlClg, ligand, and NiL^ complex mixtures. Table 11. 100 Z^Al NMR data for various AlCl2Et, ligand, and NiL^ complex mixtures Table 12. 104 The final positional parameters for atoms contained in Ni with their estimated standard deviations (in parentheses) Table 13. 105 Bond distances(A) and their estimated standard deviations (in parentheses) for Ni(6_)4 . Table 14. 106 Bond angles (°) and their estimated standard deviations (in parentheses) for Ni(_^)4 Table 15. 107 Thermal parameters and their estimated standard deviations (in parentheses) for Ni(6_)4 Table 16. 123 Final positional parameters and their estimated standard deviations (in parentheses) for meso-(CcHc)3C(0) P[CH2C(CH3)2H]2CH2 (30) Table 17. 125 Bond distances (&) and their estimated standard deviations (in parentheses) for meso-(CRHi^)iC(0)P[CHpC(CH'^)H]9CH9 Table 18. 126 Bond angles (°) and their estimated standard deviations (in parentheses) for meso-(CAHi;)qC(0)P[CH9C(CHq)H]9CHp (30) VI Table 19. 127 Thermal parameters and their estimated standard deviations (in parentheses) for meso-(Cf;H^)ciC(0)P[CHpC(CH"()H]9CH9 (30) Table 20. 133 NMR chemical shifts for selected phosphorinane compounds Table 21. 140 The preparation of adiponitrile from butadiene and HCN using various catalyst systems at 120° in xylene Table 22. 146 The number of turnovers per unit time produced by various [Ni(23)(L)g]p polymers versus their homogeneous NiL^ complexes for the isomerization of 3-butenenitrile Table 23. 151 Amount of H'^'/nickel found in NiL^/XN-lOlO resin catalysts Table 24. 152 Number of turnovers/unit time of supported NiL^ complexes, versus their homogeneous analogue for the isomerization of 3- butenenitrile Table 25. 165 Bond distances (A), angles (°), and their standard deviations for Me2NP(0CH2)2CMe2 (20) Table 26. 166 Bond distances (A), angle (°), and their standard deviations for CH2(CH2CH2)NP(0CH2)CMe2 (21) Table 27. 167 Final positional parameters and their standard deviations for Me2NP(0CH2)2CMe2 (^) Table 28. 168 Final positional parameters and their standard deviations for CH2(CH2CH2)2NP(0CH2)2CMe2 (21) vil Table 29. 169 Final thermal parameters and their standard deviations (in parentheses) for Me2NP(0CH2)2CMe2 (20) Table 30. 170 Final thermal parameters and their standard deviations (in parentheses) for CH2(CH2CH2)2NP(OCH2)2CMe2 (^) Table 31. 180 Ionization energies Table 32. 184 NMR chemical shifts (ppm) and Joi 77 coupling constants (Hz) 31p.77se Table 33. 193 Phosphorus chemical shifts of model compound derivatives Table 34. 197 Phosphorus chemical shifts of 1,3,2-dioxaphospholanyl derivatives of various alcohols (OCH2CH2OP-OR) Table 35. 198 Comparison of ratios of peak areas of 1,3,2-dioxaphospholanyl derivatives (OCH2CH2OPOR) to PPhg under conditions of broad band decoupling. Table 36. 199 Comparison of ratios peak areas of 1,3,2-dioxaphospholanyl derivatives (OCH2CH2OPOR) to PPhg under conditions of gated decoupling. Table 37. 200 Results of ^^P NMR analysis of alcohol mixtures using _1£ as a derivatizing reagent, PPhg as an internal standard, and broad band decoupling VI11 Table 38.