Theoretical study of the reaction of Cu+ with OCS

The reactivity of Cu+ with OCS on both singlet and triplet potential energy surfaces (PES) has been investigated at the UB3LYP/6-311+G(d) level. The object of this investigation was the elucidation of the reaction mechanism. The calculated results indicated that both the C-S and C-O bond activations proceed via an insertion-elimination mechanism. Intersystem crossing between the singlet and triplet surfaces may occur along both the C-S and C-O bond activation branches. The ground states of CuS+ and CuO+ were found to be triplets, whereas CuCO+ and CuCS+ have singlet ground states. The C-S bond activation is energetically much more favorable than the C-O bond activation. All theoretical results are in line with early experiments.