Applying the ligand electrochemical parameter approach to sandwich complexes and standardizing to the Fe(III)/Fe(II) couple, we obtained E(L)(L) values for over 200 pi-ligands. Linear correlations exist between formal potential (E degrees ) and the summation operatorE(L)(L) for each metal couple. In this fashion, we report correlation data for many first row transition metal couples. The correlations between the E(L)(L) of the substituted pi-ligand and the Hammett substituent constants (sigma(p)) are also explored.

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Emphasis is given to redox, photophysical, and photochemical properties of homologous bent metallocenes of group 4 transition metals. Comparative analysis of a variety of electron-transfer induced transformations and ligand-to-metal charge-transfer excited states is performed for bent metallocene complexes upon systematic variation of the identity of the metal ion (Ti, Zr or Hf), ancillary π- and monodentate σ- (Cl, Me) ligands. For such organometallic π-complexes, linear correlations exist between energies of optical and redox HOMO-to-LUMO electron transitions. It is suggested that combination of spectroscopic and electrochemical techniques provides important diagnostics to determine "ionisation potential" and "electron affinity" in solution (relative energies of frontier molecular orbitals obtained as redox potentials) and the energy gap in metallocene complexes. Some of earlier instructive cases of direct relationship between optical transition energies and differences in redox potentials revealed for inorganic and coordination compounds are discussed.

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