Cl(3)V(mu-S(CH(3))(2))(3)VCl(3)(2)(-): a first-row, face-shared bioctahedral complex with multiple metal-metal...

Density functional theory calculations have been used to investigate the structure and bonding of the d(3)d(3) bioctahedral complexes X(3)V(mu-S(CH(3))(2))(3)VX(3)(2)(-) (X = F(-), Cl(-), OH(-), SH(-), NH(2)(-)). According to geometry optimizations using the broken-symmetry approach and the VWN+B-LYP combination of density functionals, the halide-terminated complexes have a V-V bond order of approximately 2, while complexes featuring OH(-), SH(-), or NH(2)(-) as terminal ligands exhibit full triple bonding between the vanadium atoms. The tendency toward triple bonding in the latter complexes is consistent with an increased covalency of the vanadium-ligand bonds, and the influence of bond covalency is apparent also in the tendency for V-V bond elongation in the complexes with OH(-) and NH(2)(-) terminal ligands. Detailed examination of the composition of molecular orbitals in all of the thioether-bridged V(II) complexes substantiates the conclusion that the strong antiferromagnetic coupling which we have determined for these complexes (-J > 250 cm(-)(1)) is due to direct bonding between metal atoms rather than superexchange through the bridging ligands. As such, these V(II) complexes comprise the first apparent examples of multiple metal-metal bonding in first-transition-row, face-shared dinuclear complexes and are therefore of considerable structural and synthetic interest.