The mechanisms for the photochemical CO-dissociation and the oxidative addition reactions are studied theoretically using three model systems: M(CO)5 (M = Fe, Ru, and Os) and the CASSCF/Def2-SVP (fourteen-electron/ten-orbital active space) and MP2-CAS/Def2-SVP//CASSCF/Def2-SVP methods. The structures of the intersystem crossings and the conical intersections, which play a decisive role in these CO photo-extrusion reactions, are determined. The intermediates and the transition structures in either the singlet or triplet states are also computed, in order to explain the reaction routes. These model studies suggest that after the irradiation of Fe(CO)5 with UV light, it quickly loses one CO molecule to generate a 16-electron iron tetracarbonyl, in either the singlet or the triplet states. It is found that the triplet Fe(CO)4 plays a vital role in the formation of the final oxidative addition product, Fe(CO)4(H)(SiMe3), but the singlet Fe(CO)4 plays a relatively minor role in the formation of the final product. However, its vacant coordination site interacts weakly with solvent molecules ((Me3)SiH) to yield the alkyl-solvated iron complexes, which are detectable experimentally. The theoretical observations show that Ru(CO)5 and Os(CO)5 have similar photochemical and thermal potential energy profiles. In particular, this study demonstrates that the oxidative addition yield for Fe is much greater than those for its Ru and Os counterparts, under the same chemical conditions.
This journal is © The Royal Society of Chemistry.