Flash Communication: Unexpected Oxidative Alkene Cleavage Behavior of a Molecular Molybdenum Bis(dithiolene) Catalyst

Whereas homogeneous molybdenum catalysis typically promotes alkene epoxidation with peroxide oxidants, here, a molybdenum bis(dithiolene) compound is shown to instead catalyze oxidative alkene cleavage, resulting in carbonyl products akin to ozonolysis reactions. A mechanism involving O2 transfer from a Mo(O)(η2-O2) intermediate to the alkenes to form 1,2-dioxetanes is proposed with support from DFT calculations.尽管均相钼催化通常以过氧化物作为氧化剂实现烯烃环氧化，但本研究发现双(二硫烯)钼化合物可转而催化烯烃发生氧化裂解，生成与臭氧化反应类似的羰基产物。研究提出了一条由Mo(O)(η2-O2)中间体向烯烃转移氧以生成1,2-二氧杂环丁烷的反应机理，并通过密度泛函理论(DFT)计算为该机理提供了支撑。