Lantern-Type Divanadium Complexes with Bridging Ligands: Short Metal-Metal Bonds with High Multiple Bond Orders.

Vanadium forms binuclear complexes with a variety of ligands often containing V≡V triple bonds. Many tetragonal divanadium paddlewheel complexes with bridging bidentate ligands have been experimentally characterized. This research exhaustively treats model tetragonal, trigonal, and digonal paddlewheel-type divanadium complexes V L (L=formamidinate, guanidinate, and carboxylate; x=2, 3, 4), each in the three lowest-energy spin states. The V-V formal bond orders are obtained from metal-metal MO diagrams for representative structures. A number of short V-V multiple bonds of order 3, 3.5, and 4 are found in these model complexes. The short V≡V triple bonds and singlet ground state predicted here for the model tetragonal complexes correspond well with the limited experimental results for the series of known tetragonal paddlewheels. Digonal divanadium lanterns with very short V-V quadruple bonds are predicted as interesting synthetic targets. The V-V bond distances are categorized into distinct ranges according to the formal bond order values from 0.5 to 4. These bond length ranges are compared with the ranges compiled for other divanadium complexes including carbonyl complexes.