Electronic structure and metal–metal bonding in nominal d3 d3 MIIMIVCl93− (MII = V, Nb, Ta; MIV = Mn, Tc, Re) face-shared binuclear complexes
Abstract
Density functional theory (DFT) calculations have been employed to study structural and electronic configuration trends in the series of mixed-group, face-shared, bimetallic complexes M′M″Cl93− (M′
= V, Nb, Ta; M″
= Mn, Tc, Re), in which each metal possesses a nominal d3 valence electronic configuration. While the tendency of complexes to exhibit either multiple metal–metal bonded structures (with short intermetallic separations) or weakly-coupled systems (characterized by large intermetallic distances) is broadly consistent with that seen in our earlier studies on same-group dimers (e.g. Cr2Cl93−), there are also several novel structural and electronic effects which are directly attributable to