Publication Date


Document Type


First Advisor

Mason, W. Roy

Degree Name

M.A. (Master of Arts)


Department of Chemistry


Organogold compounds


Several problems in gold chemistry were investigated in this study. The first deals with the redox reaction between the tetrachloroaurate(III) anion with triphenylphosphine. The overall redox reaction is given below: AuCl⁻₄ + 2P(C₆H₅)₃ → Au[P(C₆H₅)₃]Cl + P(C₆H₅)₃Cl₂ + Cl⁻ The kinetic study of this redox reaction in acetonitrile, acetone, and dichloromethane shows that it is first-order in AuCl4 and P(C6H5)3. The kinetic data were compared with rates of related reactions of AuC14 with As(C6H3)3 and Sb(C6H5)3 in these aprotic solvents. In the present work, the reaction was studied using stopped-flow kinetic techniques. A second problem investigated includes the synthesis and substitution reactions of linear two-coordinate Au(I) complexes. The preparation and identification of a series of five Au(I) complexes using Methyl-2,6,7-trioxa-l-phosphabicyclo[2.2.2]octane (ETPB) as the entering ligand are described. The five new monomeric complexes, characterized by electronic and infrared spectra, were isolated and identified: [Au(CH₃CN)(ETPB)]ClO₄, [Au(ETPB)₂]ClO₄, [Au(ETPB)₄]ClO₄, Au(ETPB)Cl, and Au(ETPB)Br. Evidence for the successive formation of the first three complexes in acetonitrile solution is considered and their stabilities discussed. The formation constant for Au(ETPB)⁺₄ from Au(ETPB)⁺₃ in acetonitrile was determined, K₄ = 6.6 x 10³ M̲⁻¹ at 25°. Using stopped-flow instrumentation, various attempts were made to measure rates of substitution by a replacing ligand in linear Au(I) complexes. Substitution reactions of a variety of Au(I) substrates including Au(ETPB)Cl, Na₃[Au(S₂O₃)₂]·2H₂O, Au [P(C₆H₅)₃]Cl, and [Au(CH₃CN)₂]ClO₄ were surveyed using several nucleophiles such as Cl⁻, Br⁻, SCN⁻, and CN⁻. An examination of the problems encountered and the attempts to resolve them are also presented. Finally, in order to facilitate the collection of data for rapid kinetic studies, a datalog instrument was constructed as a modification to a Durrum-Gibson stopped-flow spectrophotometer model D-110 with temperature jump accessory. The construction and operation of the datalog instrument, complete with a typical example of a kinetic experiment, are described in the Appendix.


Includes bibliographical references.||Includes illustrations.


vi, 54 pages




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