Decomposition of alkyl hydroperoxide by a copper(I) complex: insights from density functional theory

The B3LYP theory and scaled hypersphere search method are utilized to explore pathways of (HO)2PS2Cu-mediated CH3OOH decomposition, a model reaction of alkyl hydroperoxide with cuprous dialkyldithiophosphate [(RO)2PS2Cu]. It is found that the decomposition of CH3OOH mediated by the copper(I) complex may lead to formaldehyde and water molecules via O-O bond heterolysis and subsequent intramolecular hydrogen transfer, with retainment of the copper(I) complex. The subsequent hydrogen transfer event and formation of water may add new understanding to the (RO)2PS2Cu-mediated decomposition process of alkyl hydroperoxide. The oxygen transfer from CH3OOH to (HO)2PS2Cu moiety, as an O-O bond cleavage manner of CH3OOH, is also found to occur.

Computations suggest that (OH)2PS2Cu(I)-mediated decomposition of CH3OOH leads to formaldehyde and water molecules via O-O bond heterolysis and subsequent intramolecular hydrogen transfer, with retainment of the copper(I) complex.