Study of Molybdenum(4+) Quinoxalyldithiolenes as Models for the Noninnocent Pyranopterin in the Molybdenum Cofactor

A model system for the molybdenum cofactor has been developed that illustrates the noninnocent behavior of an N-heterocycle appended to a dithiolene chelate on molybdenum. The pyranopterin of the molybdenum cofactor is modeled by a quinoxalyldithiolene ligand (S(2)BMOQO) formed from the reaction of molybdenum tetrasulfide and quinoxalylalkyne. The resulting complexes TEA[Tp*MoX(S(2)BMOQO)] [I, X = S; 3, X = O; TEA= tetraethylammonium; Tp* = hydrotris(3,5-dimethylpyrazolyl)-borate] undergo a dehydration-driven intramolecular cyclization within quinoxalyldithiolene, forming Tp*MoX(pyrrolo-S(2)BMOQO) (2, X = S; 4, X = 0). 4 can be oxidized by one electron to produce the molybdenum(5+) complex 5. In a preliminary report of this work, evidence from X-ray crystallography, electronic absorption and resonance Raman spectroscopies, and density functional theory (DFT) bonding calculations revealed that 4 possesses an unusual asymmetric dithiolene chelate with significant thione-thiolate character. The results described here provide a detailed description of the reaction conditions that lead to the formation of 4. Data from cyclic voltammetry, additional DFT calculations, and several spectroscopic methods (IR, electronic absorption, resonance Raman, and electron paramagnetic resonance) have been used to characterize the properties of members in this suite of five Mo(S(2)BMOQO) complexes and further substantiate the highly electron-withdrawing character of the pyrrolo-S(2)BMOQO ligand in 2, 4, and S. This study of the unique noninnocent ligand S(2)BMOQO provides examples of the roles that the N-heterocycle pterin can play as an essential part of the molybdenum cofactor. The versatile nature of a dithiolene appended by heterocycles may aid in modulating the redox processes of the molybdenum center during the course of enzyme catalysis.