Molybdenum(vi) and Molybdenum(v) Complexes With N,N'-dimethyl- N,Nr'-bis(2-mercaptophenyl)ethylenediamine: Electrochemical and Electron Paramagnetic Resonance Models For The Molybdenum(vi/v) Centers of The Molybdenum Hydroxylases and Related Enzymes

Abstract

As models for the molybdenum(VI/V) centers of the molybdenum hydroxylases and related enzymes, mo 02L and MoOCIL (LH2- 7V,A/-dimethyl-Ar,Ar/-bis(2-mercaptophenyl)ethylenediamine) have been synthesized. The structure of Mo02L has been determined by X-ray crystallography. The compound crystallizes in space group P21/n, with a - 10.049 (2) A, b - 14.538 (2) A, c = 12.143 (1) A, 0 = 103.73 (1)°, and Z = 4. Mo02L is six-coordinate with approximate C2symmetry, with the two thiolate S atoms trans to one another and the two tertiary amine N atoms approximately trans to the terminal oxo groups. mo 02L undergoes reversible one-electron reduction on both the cyclic voltammetric and coulometric time sca..