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We used computational methods to explore the mechanisms of the photochemical decarbonylation and the Si-H bond activation reaction of the group 7 organometallic compounds, η 5 -CpM(CO) 3 (M = Mn and Re). The energies of both conical intersections and the intersystem crossings, which play a decisive role in these photo-activation reactions, are determined. Both intermediates and transition states in either the singlet or triplet states are also computed to furnish a mechanistic interpretation of the whole reaction paths. In the case of Mn, four types of reaction pathways (path I-path IV) that lead to the final insertion product are examined. The theoretical findings suggest that at the higher-energy band (295 nm) the singlet-state channel is predominant. As a result, the conical intersection mechanism ( i.e. , path I) prevails. However, at the lower-energy band (325 nm) the triplet-state channel occurs. In such a situation, the intersystem crossing mechanism ( i.e. , path IV) can successfully explain its CO-photodissociation mechanism. In the case of Re, on the other hand, the theoretical evidence reveals that only the singlet state-channel is superior. In consequence, the conical intersection mechanism ( i.e. , path V) can more effectively explain its photochemical decarbonylation mechanism. These theoretical analyses agree well with the available experimental observations.

rsc advances

The mechanistic investigations of photochemical carbonyl elimination and oxidative addition reactions of (η5-C5H5)M(CO)3, (M = Mn and Re) complexes