Oxo-molybdenum(VI,V,IV) complexes of the facially coordinating tris(mercaptoimidazolyl)borate ligand: Synthesis, characterization, and oxygen atom transfer reactivity

摘要

A series of monooxo-Mo(IV,V) and dioxo-Mo(VI) complexes of the "soft" tripodal ligand, sodium tris(mercaptoimidazolyl)borate (NaTmMe), have been synthesized as potential oxygen atom transfer (OAT) models for sulfite oxidase. Complexes have been characterized by X-ray crystallography, cyclic voltammetry, and EPR, where appropriate. Oxygen atom transfer kinetics of (TmMoO2Cl)-Mo-Me, both stoichiometric and catalytic, have been studied by a combination of UV-vis and P-31 NMR spectroscopies under a variety of conditions. OAT rates are consistent with previously established relationships between redox potential/reactivity and mechanistic studies. The analysis of these complexes as potential structural and functional analogues of relevance to molybdoenzymes is further discussed.