Reaction of CO 2 with Atomic Transition Metal M +/0/- Ions: A Theoretical Study.

The activation of carbon dioxide mediated by the first row 3d transition metal (TM) M+/0/- atomic ions was studied theoretically. Theoretical calculations show left-hand transition-metal ions Sc+ , Sc, Ti+ , Ti, and V can mediate oxygen atom transfer (OAT) from carbon dioxide. In the anionic system, for early transition metal ions (Sc to Cr), [OM-CO]- are more stable than [M-OCO]- , while the others favor binding formation, [M-OCO]- . TSR was observed in O atom transfer. The OAT reaction is exothermic only for the first three transition metal cations and atoms (Sc+/0 , Ti+/0 , and V+/0 ), Fe0 and all the anions except Cu- and Zn- . Furthermore, in most case, reaction enthalpy, and energy barrier of OAT for the cationic system is the highest, and the anionic system is the lowest. We discuss the performances of 18 methods on the energies and structures.