Accession Number : ADA266307


Title :   Structural Effects in Electron Transfer Reactions: Comparative Interfacial Electrochemical Kinetics for cis- Versus trans-Dioxorhenium(V)(bi)pyridine Oxidation


Descriptive Note : Technical rept. Jul 1992-Jul 1993


Corporate Author : NORTHWESTERN UNIV EVANSTON IL DEPT OF CHEMISTRY


Personal Author(s) : Zhang, Xiao L ; Hupp, Joseph T ; Danzer, Gerald D


Full Text : https://apps.dtic.mil/dtic/tr/fulltext/u2/a266307.pdf


Report Date : 29 May 1993


Pagination or Media Count : 26


Abstract : We have been exploring the proton-coupled reductions of various dioxorhenium(V) species because of the more general insights they provide into the kinetics and thermodynamics of multielectron transfer processes. The rhenium (V) complexes are also amenable, however, to proton-decoupled one-electron oxidation-both optically (via metal-to-ligand charge-transfer excitation; Our prior studies of electron transfer (ET) thermodynamics revealed a strong dependence of the Re (VI/V) formal potential on ligand substituent characteristics (most notably, substituent electron donating or withdrawing characteristics). The studies also showed-independent of ligand substituent identify-a strong dependence of E (sub f) on isomeric form cis versus trans coordination geometry. In all cases the cis form was more easily oxidize than the corresponding trans, generally by about 600mV.


Descriptors :   *CHEMICAL REACTIONS , *MOLECULAR STRUCTURE , *ELECTRON TRANSFER , METALS , OPTICAL PROPERTIES , INTERFACES , THERMODYNAMICS , EXCITATION , LIGANDS , GEOMETRY , ACTIVATION ENERGY , RHENIUM , PYROLYTIC GRAPHITE , PYRIDINES , FREE ENERGY , VOLTAMMETRY , KINETICS , CHARGE TRANSFER , DECOUPLING , ELECTROCHEMISTRY , PROTONS , ISOMERS , OXIDATION , ELECTRODES


Subject Categories : Organic Chemistry
      Physical Chemistry
      Atomic and Molecular Physics and Spectroscopy
      Solid State Physics


Distribution Statement : APPROVED FOR PUBLIC RELEASE