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Oxo−Molybdenum(VI,V,IV) Complexes of the Facially Coordinating Tris(mercaptoimidazolyl)borate Ligand:  Synthesis, Characterization, and Oxygen Atom Transfer Reactivity

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posted on 2007-06-25, 00:00 authored by Ba L. Tran, Carl J. Carrano
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 TmMeMoO2Cl, both stoichiometric and catalytic, have been studied by a combination of UV−vis and 31P 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.