The selective catalytic oxidation of alcohols is important both in laboratory and industrial production, and traditional oxidants cause environmentally lethal wastes. The development of dioxygen selective oxidation efficient has been pursued from atom-efficient, economic and environmental view of points. Using DFT calculation and ESI-MS experiments, we studied the activation of the CuCu bonded planar complex Cu₂(ophen)₂ to dioxygen and the application of the dioxygen-copper system for the selective oxidation of alcohols. For practical application and green chemistry, this catalytic system avoided the use of a large excess of base and expensive nitroxyl derivatives. In the cycle of oxidation, two oxidative dehydrogenation processes featuring superoxide/peroxide (I) and hydroperoxide (II) occurred along with a series of conformational changes of the butterfly-like Cu-complex from stretched to folded to stretched. Additionally, we characterized the role of the water molecule as a proton mediator in the dioxygen-copper system.

醇的选择性催化氧化在实验室和工业生产中都很重要，传统的氧化剂会造成对环境有害的废物。从原子效率，经济和环境的观点出发，一直致力于发展高效的双氧选择性氧化。使用DFT计算和ESI-MS实验，我们研究了Cu Cu键结合的平面络合物Cu ₂（ophen）₂对双氧的活化作用以及双氧铜系统在醇选择性氧化中的应用。对于实际应用和绿色化学而言，该催化体系避免了使用大量过量的碱和昂贵的硝酰衍生物。在氧化循环中，以超氧化物/过氧化物（I）和氢过氧化物（II）伴随着蝴蝶状Cu复合物从拉伸到折叠再到拉伸的一系列构象变化。此外，我们表征了水分子在双氧铜系统中作为质子介体的作用。