Structurally characterized one oxo–desoxo bridged Mo2–bis(dithiolene) complex and its interconversion to a discrete oxo or desoxo DMSOR model†
Abstract
A new molybdenum complex, [Et4N]2[Mo(PPh3)(mnt)2–OMo(mnt)2]·CH2Cl2·½H2O (1, mnt = maleonitrile dithiolene = S2C2(CN)2), with unique structural features was synthesized, in which the fragment {Mo(PPh3)(mnt)2–} was attached to another important {–OMo(mnt)2} moiety. The structure of 1 was formed by the association of both the oxo and desoxo motifs of the dimethylsulfoxide reductase (DMSOR) class of enzymes. This dissymmetrical binuclear complex 1 is rare, and it utilized the basic inorganic aspects to accommodate both moieties; under basic conditions, it was converted to (Et4N)2[MoO(mnt)2] (2). Similarly, when treated with PhSH and PPh3, it was completely converted to [Et4N]2[Mo(PPh3)(mnt)2(SPh)] (3) (J. Am. Chem. Soc., 2006, 128, 4196–4197). The chemistry of 1 was analyzed with regard to its synthesis, reactivity, crystal structure, and spectroscopic and photophysical properties. In addition, the results were complemented with DFT calculations.