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.

模仿钼酶（高）氯酸盐还原酶允许开发能够减少高氯酸盐的均相催化剂。在这里，我们报告了几种新型二氧化钼 (VI) 配合物，[MoO ₂ (SN) ₂ ]（SN = 双齿配体），采用 5-nitro-6-methylpyridine-2-thiolate、4-(trifluoromethyl)pyrimidine-2-thiolate， 3-chloropyridine-2-thiolate、3-methylpyridine-2-thiolate 以及文献中已知的 [MoO ₂ (PyS) ₂ ], (PyS = pyridine-2-thiolate) 作为用于高氯酸盐还原的均相催化剂。这些配合物的设计和选择是为了评估配体对催化活性的电子效应。使用 PPh ₃作为牺牲氧受体，我们跟踪了 ClO _4的还原⁻在不同的催化条件下，通过 GC-MS测定 PPh ₃向 OPPh ₃的转化间接确定。_{发现吸电子取代基降低了从 [Mo(VI)O 2} L ₂ ] 到 PPh ₃的初始氧原子转移反应的动力学势垒，这得到了使用 UV-Vis 光谱的动力学研究的支持。然而，它们的存在也会降低复合物在探索条件下的稳定性。