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

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journal contribution
posted on 29.04.2009 by Nigel J. Brookes, Alireza Ariafard, Robert Stranger, Brian F. Yates
The reaction of CO2, OCS, and PhNCO with an iridium-supported Fischer alkoxycarbene has been investigated with density functional theory. We have confirmed the mechanism for the important CO2 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.