Kinetics and mechanism of electron transfer via bridge metal-ion

✍ Scribed by Y. A. Maletin; N. G. Strizhakova

• Publisher: John Wiley and Sons
• Year: 1986
• Tongue: English
• Weight: 807 KB
• Volume: 18
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550180103

✦ Synopsis

The kinetics and mechanism of electron transfer between stable verdazyl radicals via bridge Mn(II), Co(II), Ni(II), Cu(I), and Zn ions have been studied in the range 280-330 K using the stopped-flow technique. It was found that the kinetic features of the reactions could be described in terms of the Marcus theory. The reorganization energy of the inner coordination sphere (ICS) of intermediate complexes was estimated from the reported data on the energy of release of various ligands from the ICS of similar complexes. The rest of the kinetic parameters (solvent reorganization energy, transmission coefficients, enthalpy, and entropy of activation) were determined from Marcus equations and from plots of rate constant versus temperature, "standard free energy, and polarity of the medium. It was also found that the reactions under consideration are nonadiabatic and the transmission coefficient value depends on the mean lifetimes of ligands in the ICS.