Electron Transfer Rates and Adsorption in the Electrochemistry of Cobalt-2,2'-Bipyridine, Ruthenium Ammine Thiocyanate Complexes and cis-[(C₅H₅)Fe(CO)P(C₆H₅)₂]₂

Citation

Willett, Brian Christopher (1983) Electron Transfer Rates and Adsorption in the Electrochemistry of Cobalt-2,2'-Bipyridine, Ruthenium Ammine Thiocyanate Complexes and cis-[(C₅H₅)Fe(CO)P(C₆H₅)₂]₂. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/t7fp-5z02. https://resolver.caltech.edu/CaltechTHESIS:11042019-130341164

Abstract

In Part I of this thesis, the electrochemical properties of cobalt(I)-2,2'-bipyridine and cobalt(I)-6,6'-dimethyl-2,2'-bipyridine complexes were investigated, including their reactions with reducible substrates and their adsorption on mercury electrodes.

Electron transfer rate constants measured for cyclooctatetraene and cis-[(C₅H₅)Fe(CO)P(C₆H₅)₂]₂, molecules which undergo large intramolecular rearrangements upon electron transfer, in non-aqueous solvents with various tetraalkylammonium salts as supporting electrolytes are presented in Part II. The electrode kinetics were measured by cyclic voltammetry, chronocoulometry and AC impedance techniques. Values of the rate constants found were as large as 0.30 cm/sec.

Synthesis and adsorption behavior of several novel substituted ruthenium ammine complexes are discussed in Part III. The adsorption on mercury was used to distinguish between the two thiocyanate linkage isomers, Ru(NH₃)₅NCS²⁺ and Ru(NH₃)₅SCN²⁺. The coordination properties of ruthenium(II) were used to prepare trans-Ru(NH₃)₄(NCS))4-vinyl- pyridine)Ru(EDTA), a binuclear ruthenium species.

Thesis Files