Oxo-carboxylato-molybdenum(vi) complexes possessing dithiolene ligands related to the active site of type II DMSOR family molybdoenzymes

Abstract

Spectroscopic and kinetic studies indicate that oxo-carboxylato- molybdenum(vi) bis-dithiolene complexes, (MoVIO(p-X-OBz)L 2), have been generated at low temperature as active site structural models for the type II class of pyranopterin molybdenum DMSOR family enzymes. A DFT analysis of low energy charge transfer bands shows that these complexes possess a Mo-Sdithiolene π-bonding interaction between the Mo(dxy) redox active molecular orbital and a cis S(pz) donor orbital located on one of the dithiolene ligands. © 2013 The Royal Society of Chemistry.