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Mechanistic Chemistry of Some Transition Metal Complexes Garry Wayne Kirker Iowa State University

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Mechanistic Chemistry of Some Transition Metal Complexes Garry Wayne Kirker Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1981 Mechanistic chemistry of some transition metal complexes Garry Wayne Kirker Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Kirker, Garry Wayne, "Mechanistic chemistry of some transition metal complexes " (1981). Retrospective Theses and Dissertations. 7183. https://lib.dr.iastate.edu/rtd/7183 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 was produced from a copy of a document sent to us for microfilming. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help you understand 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 you of complete continuity. 2. When an image on the film is obliterated with a round black mark it is an indication that the film inspector noticed either blurred copy because of movement during exposure, or duplicate copy. 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In all cases we have filmed the best available copy. University Microfilms International 300 N. ZEffB RD,, ANN ARBOR, Ml 48106 8122530 KIRKER, GARRY WAYNE MECHANISTIC CHEMISTRY OF SOME TRANSITION METAL COMPLEXES Iowa State University PH.D. 1981 University Microfilms Intsrnstionâl 300 Zeeb Road, Ann Arbor, MI 48106 Mechanistic chemistry of some transition metal compl by Garry Wayne Kirker 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. In Charge of Major Work Signature was redacted for privacy. Fbr the Major DepsfHment Signature was redacted for privacy. Iowa State University Ames, Iowa 1981 ii TABLE OF CONTENTS Page SYMBOLS AND CONVENTIONS xii INTRODUCTION 1 PART I. REACTIONS OF a-HYDROXYLALKYLCHROMIUM(III) COMPLEXES A, ACIDOLYSIS AND HOMOLYSIS 2 INTRODUCTION 3 General 3 Historical 4 EXPERIMENTAL 12 Materials 12 Reagents 12 Methods 16 Analyses 16 Kinetics 17 Activation parameters 19 Instrumentation 100+ 20 Photochemical generation of CrC(R R )0H 22 RESULTS 23 Characterization and Reactivity 23 Identification of organochromium complexes 23 Reaction selection 25 Acidolysis reactions 29 Homolysis reactions i p 9+ 37 Photochemical generation of CrC(R R )0H « 64 Acid rearrangement of CrC(CH2)20CH(CH2)2 64 DISCUSSION 69 Acidolysis 69 Photochemical Syntheses 74 Homolysis 76 iii B. REACTIONS WITH Cu^^ OR 95 INTRODUCTION 96 EXPERIMENTAL 98 Materials 98 Reagents 98 Methods 99 Analyses 99 Kinetics 99 RESULTS 100 DISCUSSION 115 PART II, BINUCLEAR COBALT COMPLEXES OF SCHIFF BASE MACROCYCLIC LIGANDS 124 INTRODUCTION 125 EXPERIMENTAL 129 Materials 129 Substituted salicylaldehydes 129 Ligands 131 Cobalt complexes 133 Inorganic reagents 137 Methods 138 Analyses 138 Stoichiometries 139 Kinetics 139 Instrumentation 141 RESULTS 142 Reactions of the Binuclear Complexes 142 Reaction of Co^^^fS-Bu^sal^bz)^* with CrClg 142 Reaction of Co|^^(S-SOgSal^bz)^" with CrCl2 147 Reaction of Co^^(5-Bu^sal^bz) with oxidants 150 iv Organometallic compound formation and reactivity 154 DISCUSSION 161 BIBLIOGRAPHY 171 ACKNOWLEDGEMENTS 178 V LIST OF TABLES Page Table I-l. Purification of organic reagents 15 Table 1-2. Estimation of steady-state radical concentrations under some acidolysis conditions 27 Table 1-3. Sunmary of acidolysis values at 25.0°C 36 Table 1-4. Sunmary of activation parameters for acidolysis of CrC(R,RT)0H^^ complexes 39 Table 1-5. The kinetics of reaction of CrCfCHgjfCgHgjOH^^ under acidolysis conditions 40 Table 1-6. The kinetics of reaction of CrCfCgHgjgOH^^ under acidolysis conditions 41 Table 1-7. The kinetics of reaction of CrCCCH^)(i-C^H^jOH^^ under acidolysis conditions 41 Table 1-8. Summary of acidolysis and homolysis rate constants for CrCHfCgHgjOH^* 42 Table 1-9. Rate constants for homolysis of CrC(R^R^)0R^^ complexes 44 Table I-IO. Sunmary of the activation parameters for the homolysis reaction 46 Table I-ll, Range of oxidants used to study the homolysis reaction of CrCfCHgifCgHglOHZ* 47 Table 1-12. Variation of k^^^ with temperature for CrC(CH3)20H2+ 48 Table 1-13. Variation of k^om CrCCCH^)(C2Hg)0H^^ as a function of temperature 49 Table 1-14. Range of oxidants used to study the homolysis reaction of CrC(C2Hg)20H^* 50 Table 1-15. Homolysis data for CrC(C2Hg)20H^* 50 vi Table 1-16. Range of oxidants used to study the hotnolysis reaction of CrCfCHgifi-CgHyiOHZ* 57 Table 1-17. Variation of with temperature for CrC(CH3)(t-C4Hg)0H^"^ 57 Table 1-18. Variation of k^om with temperature for CrC(CH3)20CH(CH3)2^'^ 58 Table 1-19. The kinetics of reaction of CrC(CH2)20CH(CH2)2^^ under acidolysis conditions 67 Table 1-20. Comparison of acidolysis rate constants for complexes of similar steric bulk 70 Table 1-21. Thermodynamic parameters for the hemolysis reaction: CrC(R^R^)OR^'^ v=^pCr^'^ + •C(R^R^)OR 78 Table 1-22. Estimation of the steric strain in CrC(R^,R^)OR^* complexes 88 Table 1-23. Taft substituent effect 91 Table 1-24. Kinetic data for the reaction of Cu^^ with CrCH(C2Hg)0H^"^ 101 Table 1-25. Kinetic data for the reaction of Fe^^ with CrCH(C2H5)0H2+ 102 2+ Table 1-26. Kinetic data for the reaction of Cu with CrC(CH3)(C2H5)0H^"^ 103 Table 1-27. Kinetic data for the reaction of Fe^* with CrC(CH3)(C2Hg)2+ 104 Table 1-28. Kinetic data for the reaction of Cu^^ with CrC(C2H5)20H^'^ 105 3+ Table 1-29. Kinetic data for the reaction of Fe with CrC(C2H5)20H^'^ 106 vil ?+ Table 1-30. Kinetic data for the reaction of Cu with CrC(CH2)(i-C2Hy)0H2+ 107 Table 1-31. Kinetic data for the reaction of Fe^* with CrC(CH2)(i-C3Hy)0H2+ 108 Table 1-32. Parameters for the dependence of oxidation rate constants on [H*] 109 Table II-l. Electronic spectra of the ligands and cobalt complexes 140 Table II-2. Rate constants for the reaction of CrClg with (Colli)(S-SOgSalgjbz 148 Table II-3. Rate constants for the reaction of oxidants with (CoIIIjgfS-Butsal^bz) at 25° 152 P+ Table I1-4. Rate constants for the reaction of Hg with (CHgCoOgfS-Butsal^bz) 158 viii LIST OF FIGURES Page Figure I-l. Schematic diagram of the D-132 multi-mixing system 21 Figure 1-2. Electronic spectrum of (HpO)rCrC(CHg)(CpHr)OH^*, (£ = 1 cm), ^10"^ M 24 Figure 1-3. Plot of log |D-D^| versus time for decomposition of CrCH(C2Hg)0H2+ under acidolysis conditions at 0.5 M HCIO4. 25°C, u = 1.00 M (LiClO^) 30 Figure 1-4, Plot of log |D-D^| versus time for decomposition of CrCCCH^)(C2Hg)0H under acidolysis conditions at 0.098 M HCIO4, 25.0°C, y = 1.00 M (LiClO^) 31 Figure 1-5. Plot of k/\ versus [H^] for acidolysis reactions of CrCH{C2Hg)0H^'^ at 25°C, y = 1,00 M (LiClO^) 32 Figure 1-6. Plot of versus [H^] for acidolysis reactions of CrCfCH^jfCgHgiOH^^ at 15.0, 25.0 and 34.8°C, y = 1,00 M (LiClO^) 33 Figure 1-7. Plot of versus [H^] for acidolysis reactions of CrC(CH2)(i-C2Hy)0H2+ at 15.1, 25.0 and 35.1°C, y = 1.00 M (LiClO^) 34 Figure 1-8. Plot of versus [H*] for acidolysis reactions of CrC{C2Hg)20H^"^ at 20.0, 25.0 and 35.0°C, y = 1.00 M (LiClO^) 35 Figure 1-9. Eyring plots for the decomposition of CrC(CH3)(C2Hg)0H2+ (0) and CrC(C2Hg)20H2+ (.) under acidolysis conditions at 1 M HCIO^ 38 Figure I-IO. Eyring plot for the decomposition of CrCfCH^jgOH^^ under homolysis conditions 51 Figure I-ll. Eyring plot for the decomposition of CrC(CH2)(C2Hg)0H^^ under homolysis conditions 52 ix Figure 1-12. Plot of versus [Oxidizing Scavenger] for reactions of CrCfCHgjfCgHgjOH^* with the oxidants: Fe3+ (•), Cu2+ (e), H,0, (o), Co(NH_)rCl2+ (e), and Co(NH2)gBr2+ (A) 53 Figure 1-13.
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