Fig. 29.

Reaction mechanisms of CarO as proposed based on DFT calculations, adapted from [169]. Only the catalytically relevant substructure of the polyene substrate is shown. The lowest energy pathways found proceed via a dioxetane- (path 1) and an epoxide-intermediate (path 2), respectively. The pathway in the presence of water is depicted. Both reaction pathways have been calculated in the presence and absence of metal-bound water, with similar results, however, in the absence of water the side on addition of O₂ porceeds via one concerted step (path 1a*, dashed arrow).