Abstract

The aerobic photocatalysed oxidation of alkanes in the presence of decatungstates Q4W10O32(Q = Na, Me4N, Pr4N, Bu4N, Hex4N) leads to hydroperoxides as primary products. Nitrile solvents and organic counter-ions of the catalyst compete in this photooxidation with alkane substrate. The influence of this competition on quantum yield, rate and selectivity for the oxidation of adamantane is quantitatively evaluated. A catalytic cycle, describing the formation of primary and secondary oxidation products, is proposed.

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