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 O 2 transfer from a Mo(O)(η 2 -O 2 ) intermediate to the alkenes to form 1,2-dioxetanes is proposed with support from DFT calculations.