Cleavage of Carbon Dioxide by an Iridium-Supported Fischer Carbene. A DFT Investigation

摘要

The reaction of CO_2, OCS, and PhNCO with an iridium-supported Fischer alkoxycarbene has been investigated with density functional theory. We have confirmed the mechanism for the important CO_2 reaction and successfully rationalized the selective cleavage of the CS and CN bonds in OCS and PhNCO. Armed with this information we have used our model to predict that the same iridium system will preferentially cleave the CS bond in methyl thiocyanate (MeNCS) rather than the CN bond. The formation of the iridium-supported carbene itself has also been investigated and a fascinating autocatalytic mechanism has been discovered which nicely fits the observed experimental behavior.