Redox orbital prediction

Lever has successfully predicted Mn"/ potentials of 24 Mn-carbonyl complexes containing halide, pseudohalide, isonitrile, and phosphine co-ligands, with additivity parameters derived from the potentials of Ru "/" couples [39]. An important consideration for heteroleptic complexes is the influence of isomerism on redox thermodynamics. For Mn(CO) (CNR)6- complexes, with n = 2 or 3, the Mn"/ potentials for cis/trans and fac/mer pairs differ by as much as 0.2 V [40]. The effect arises from the different a-donor and 7r-acceptor abilities of carbonyl (CO) and isocyanide and their influence on the energy of the highest energy occupied molecular orbital (HOMO). 

It has been found that whereas Cu11 porphyrins luminesce, the Ag" complexes do not. By an examination of electronic absorption spectra, emission spectra, redox potentials and near-IR absorption data, it was proposed that this could be rationalized on the basis of the energy of the big (dx2 yi) orbital. Extended Hiickel molecular orbital calculations predicted that the d-n transition would be above the lowest (n, jt ) levels for Cu11 but below them in the Agn complexes. The near-IR absorptions found for Ag11 were attributed to CT transitions.554... 

Semiempirical MNDO calculations have been carried out on model pyrylium and thiopyrylium systems (88MI1). The calculated HOMO-LUMO gap in the gas phase correlates well with experimental absorption maxima obtained in solution. Ionization potentials and electron affinities predicted by Koopmans theorem with MNDO orbital energies do not track the observed trends in the experimental redox values. In contrast these are paralleled by the trends predicted by A// values calculated by MNDO and AMI for the open-shell and closed-shell species. 

This chapter considers the oxidation of iodide in seawater by natural oxidants (02, H202, and 03). The oxidation of iodide to iodate is considered slow, yet the six-electron T-IOj redox couple normally used to represent the process (or predict stability) is thermodynamically favorable (2). We will discuss both one- and two-electron-transfer processes with these oxidants, focusing on the first step of electron transfer and using the frontier molecular orbital theory approach in conjunction with available thermodynamic and kinetic data. The analysis shows that the chemical oxidation of I to I03 is not a very important process in seawater, except perhaps at the surface microlayer. 

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