Abstract
Mimicking the molybdoenzyme (per)chlorate reductase allows for the development of homogeneous catalysts capable of reducing perchlorate. Here, we report several novel dioxidomolybdenum(VI) complexes, [MoO2(SN)2] (SN = bidentate ligand) employing 5-nitro-6-methylpyridine-2-thiolate, 4-(trifluoromethyl)pyrimidine-2-thiolate, 3-chloropyridine-2-thiolate, 3-methylpyridine-2-thiolate as well as the literature-known [MoO2(PyS)2], (PyS = pyridine-2-thiolate) as homogeneous catalysts for perchlorate reduction. These complexes were designed and chosen to evaluate the electronic effect of the ligands on the catalytic activity. Using PPh3 as a sacrificial oxygen acceptor, we followed the reduction of ClO4− indirectly by the determination of the conversion of PPh3 to OPPh3 by GC–MS, under different catalytic conditions. Electron-withdrawing substituents were found to reduce the kinetic barrier for the initial oxygen atom transfer reaction from [Mo(VI)O2L2] to PPh3 supported by kinetic investigations using UV–Vis spectroscopy. However, their presence also decreases the stability of the complexes under the explored conditions.
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