Electron transfer characterization of iron and cobalt porphyrins and copper complexes, and of their metal-carbon and metal-oxygen bond energies
The electron-transfer and oxidation-reduction chemistry for the alkyl-iron and alkyl-cobalt porphyrins [(Por)M-R] and copper complexes has been investigated on the basis of cyclic voltammetric and controlled-potential-electrolysis measurements. Half-wave potentials for the oxidation and the reduction of (Por)M-R are directly influenced by the nature of the electron-donating or electron-withdrawing groups on the porphyrin ring and the structure of the alkyl groups. The redox potentials for a series of copper complexes are affected by the electron donating ability and the chelate effect of the ligands. Hydrolysis of the copper(II) cations (Cu{sup II}L{sub n}{sup 2+}) occurs in water. The reactivity of copper(I) complexes with dioxygen is directly related to the oxidation potential of the complexes in the solvent. The combination of Cu{sup I}(bpy)2{sup +} and tertiary-butyl hydroperoxide induces O{sub 2} activation to oxygenate methylenic carbon to ketones. Mechanistic schemes have been developed on the basis of electrochemical and spectrophotometric characteristics and reaction-product profiles for copper(II)-bis(bipyridine) [Cu{sup II}(bpy)2{sup 2+}]/base-induced activation of O{sub 2} to dehydrogenate primary alcohols to aldehydes. The free energies of bond formation (-{Delta}G{sub BF}) for the (Por)M-R and copper-ligand (oxygen or nitrogen) bonds have been determined from the redox potentials of the corresponding electrode reactions. The values of -{Delta}G{sub BF} are 14-35 kcal mol{sup {minus}1} for iron porphyrins and 20-38 kcal mol{sup {minus}1} for cobalt porphyrins which depend on the structures of the porphyrins and the alkyl groups. Apparent bond energies are 18-51 kcal mol{sup {minus}1} for the Cu{sup II}-L bonds are 46-78 kcal mol{sup {minus}1} for the Cu{sup I}-L bonds. The free energies of bond formation for the L{sub n}Cu{sup I}-OO bonds are 7-16 kcal mol{sup {minus}1}.
- Research Organization:
- Texas A and M Univ., College Station, TX (United States)
- OSTI ID:
- 111303
- Resource Relation:
- Other Information: TH: Thesis (Ph.D.); PBD: 1992
- Country of Publication:
- United States
- Language:
- English
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