Investigations of the Binding of Some Azido-, Isocyano-, and Isothiocyanatochromium(III) and Azidocobalt(III) Complexes with Heavy Metal Ions and Mercury Electrodes

Citation

Frank, Steven Neil (1974) Investigations of the Binding of Some Azido-, Isocyano-, and Isothiocyanatochromium(III) and Azidocobalt(III) Complexes with Heavy Metal Ions and Mercury Electrodes. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/H0WX-5123. https://resolver.caltech.edu/CaltechETD:etd-10132005-083002

Abstract

NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. Part I. -- The reactions of [...], [...], and [...] with [...] and [...] to form binuclear and trinuclear adducts have been investigated. Equilibrium quotients evaluated include: [...]; [...]; [...]; [...]. Electrochemical reduction of the heavy metal adducts was utilized to generate a variety of the unstable isocyanochromium(III) isomers at mercury electrodes. No adsorptive binding of any of these complexes to the surface of the mercury electrodes could be detected. Possible reasons for the contrasting behavior displayed by the (nonadsorbing) isocyanochromium(III) and (strongly adsorbing) isothiocyanato chromium (III) complexes are examined. Part II. -- The adsorption at mercury electrodes of a number of azido- and thiocyanatochromium(III) and azidocobalt(III) complexes has been measured with chronocoulometry. Apparent attractive interactions between adsorbed molecules were observed for the thiocyanato-complexes at some coverages. Several possible explanations are advanced to account for this behavior. A correlation between the amounts of adsorption and the ligand field stabilization energies (LFSE) of the complexes was observed. This correlation is discussed in terms of an increase in the LFSE when the complexes bind with the electrode.

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