Electrochemical Parameterization of Metal Complex Redox Potentials, Using the Ruthenium (III)/Ruthenium(II) Couple to Generate a Ligand Electrochemical Series
YORK UNIV DOWNSVIEW (ONTARIO) DEPT OF CHEMISTRY
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A ligand electrochemical parameter, El L, is described to generate a series which may be used to predict MnMn-1 redox potentials by assuming that all ligand contributions are additive. In this fashion it performs a similar purpose to the Dq parameter in electronic spectroscopy. The parameter is defined as 16 that of the RuIIIRuII potential for species RuL6 in acetontrile. The ElL values for over 200 ligands are presented and the model is tested over a wide range of coordination complexes and organometallic species. The redox potential of a MnMn-1 couple is defined to be equal to- Ecalc f Sigma EL L c. The values of f and C, which are tabulated, depend upon the metal and redox couple, and upon spin state and stereochemistry, but, in organic solvents, are generally insensitive to the net charge of the species. Consideration is given to synergism, the potentials of isomeric species, and the situations where the ligand additivity model is expected to fail. In this initial study, the redox couples are restricted almost exclusively to those involving the loss or addition of an electron to the tzg in Oh sub-level.
- Organic Chemistry
- Physical Chemistry