Abstract
Abstract Novel mono(dithiolato) molybdenum(VI) and tungsten(VI) complexes were isolated through the searching for potential active species in the catalytic air oxidation of benzoin by [MoVO(SR)4]− complexes. Among these, (NEt4)2[{MoVIO2(3-triphenylsilyl-1,2-benzenedithiolato)}2(μ-O)]·2DMF (1), (PPh4)2[{WVIO2(1,2-benzenedithiolato)}2(μ-O)] (3), and (NEt4)2[{WVIO2(2,3-naphthalenedithiolato)}2(μ-O)] (5) were structurally characterized by X-ray crystallography. The electrochemical, electronic, as well as Raman/IR spectral properties of the tungsten complexes, 3 and 5, have been investigated and compared with the corresponding bis(dithiolato) complexes, e.g. [WVIO2(dithiolato)2]2−. The μ-oxo-binuclear species, [{MoVIO2(SR)2}2(μ-O)]2−, is proposed as a possible active species for the catalytic air oxidation of benzoin by the Mo(V) thiolato complexes.
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