Theoretical study of terminal anadium(v) chalcogenido complexes bearing chlorido and methoxido ligands

Abstract

Solvent (methanol) coordinated anadium(V) chalcogenido complexes bearing chlorido and methoxido ligands have been studied computationally by means of density functional (DFT) methods. Te gas phase complexes were fully optimized using B3LYP/GEN functionals with 6-31+G ∗∗and LANL2DZ basis sets. The optimized complexes show distorted octahedral geometries around the central vanadium atom. The ligand p-vanadium d interactions were analyzed by natural bond order (NBO) and natural population analyses (NPA). These results show strong stabilization of the V=O bond as was further confirmed by the analyses of the frontier molecular orbitals (FMOs). Second-order perturbation analyses also revealed substantial delocalization of lone pair electrons from the oxido ligand into vacant non-Lewis (Rydberg) orbitals as compared to the sulfdo and seleno analogues. These results show significant ligand-to-metal charge transfer (LMCT) interactions. Full interaction map (FIM) of the reference complex confirms hydrogen bond interactions involving the methanol (O-H) and the chlorido ligand