Date

November 1980

Document Type

Dissertation

Degree Name

Ph.D.

Department

Dept. of Chemistry and Biochemical Sciences

Institution

Oregon Graduate Center

Abstract

Copper (I) forms π complexes with olefin-containing metal complexes in aqueous solution. Reduction of a series of pyridinepentaammineruthenium (III) ions, where L is a pyridine or 4-substituted pyridines, was studied. For the (NH[subscript 3]) [subscript 5] Ru (III)-4-viny1pyridine ion it is possible to measure separately preequilibrium binuclear ion formation and electron transfer. The electron transfer pathway is determined to be intramolecular from comparison with rate behavior of (NH[subscript 3]) [subscript 5] (III)-4-ethylpyridine, Cu (I) and (NH[subscript 3]) [subscript 5] (III)-pyridine, Cu (I) redox pairs. Rate parameters are also determined for the reverse reaction. Cu (II) catalyzed autoxidation of the (NH[subscript 3]) [subscript 5] (II) - 4-vinylpyridine ion. The redox equilibrium constant determined from the kinetic data agrees reasonably with that calculated from the redox potentials of the reactants. Qualitative models have been advanced from which it is suggested that the entropy of activation gives a measure of the probability for electron transfer in the activated complex, values near zero indicating that electron-tunneling is not rate-limiting. Cu(I)-olefin containing binuclear ions of (NH[subscript 3])[subscript 5]Co(III)L, where L is an alkylpyridine or alkylamine, undergo efficient intramolecular electron transfer when irradiated in the Cu(I)-olefin(n*) absorption band. The results of photoredox studies of a series of alkylamine and alkylpyridine containing binuclear ions are reported. The quantum yields for Co (II) production is shown to falloff monotonically for increasing number of methylene carbons in the chain. Binuclear ions containing polyisoprenyl bridging ligands were also investigated. Mixed solvent studies show decreased quantum yield with increasing ethanol content of the aqueous media. Medium and chain configuration effects are discussed.

Identifier

doi:10.6083/M4C24TC9

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.