Electronic interactions between metals and dithiolenes are important in many metalloenzymes and in diverse chemical and material applications. To better understand metal-dithiolene electronic interactions, new capabilities in gas-phase core photoelectron spectroscopy for molecules with high sublimation temperatures have been developed and applied to the series of molecules Cp2M(bdt), where Cp = ?5-cyclopentadienyl, M= Ti, V, Mo, and bdt = benzenedithiolato. Comparison of the gas-phase core and valence ionization energy shifts provides a unique quantitative energy measure of valence orbital overlap interactions between the metal and the sulfur orbitals that is separated from the effects of charge redistribution. The results explain the large amount of sulfur character in the redox-active orbitals and the 'leveling' of oxidation state energies in metal-dithiolene systems. The experimentally determined orbital interaction energies also reveal a previously unidentified overlap interaction of the predominantly sulfur HOMO of the bdt ligand with filled p orbitals of the Cp ligands.

Metal-sulfur valence orbital interaction energies in metal-dithiolene complexes: Determination of charge and overlap interaction energies by comparison of core and valence ionization energy shifts

243rd National Meeting (2012)

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