Electron distribution in the nonclassical bis(dithiolene) electron transfer series [M(CO)2(S2C2Me2)2]0/1-/2- (M = Mo,...

The electron-transfer series [M(CO)2(S2C2Me2)2]0/1-/2- (series 2) have been established, and the previously reported series [M(S2C2Me2)3]0/1-/2- (series 3) confirmed, by voltammetry (M = Mo, W). Redox reactions are reversible with EMo > EW, and all members of each series have been isolated. Members of a given series have very similar distorted trigonal prismatic structures; isoelectronic complexes are isostructural. The existence of these series with structurally characterized members facilitates examination of geometric and electronic properties over three consecutive oxidation states. Upon traversing the series in the reducing direction, M-S, S-C, and C-O bond distances increase, and M-C, chelate ring C-C, and vCO values decrease. Density functional calculations identify the electroactive orbital, which is well separated in energy from other orbitals. Trends in bond lengths and vibrational frequencies in a given series are fully accountable in terms of increasing population of this orbital, whose composition is roughly constant across the series and is dominantly ligand (ca. 80%) in character. Consequently, redox reactions in the two series are essentially ligand-based. The noninnocent nature of dithiolene ligands in oxidized complexes has been long recognized. The results of DFT calculations provide a contemporary description of the delocalized ground states in the two series. The trends in parameters involving the carbonyl groups provide a particularly clear indication of the classical behavior of a pi-acceptor ligand in isostructural molecules subject to consecutive reductions over three oxidation states.