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 iridiumsupported carbene itself has also been investigated and a fascinating autocatalytic mechanism has been discovered which nicely fits the observed experimental behavior. © 2009 American Chemical Society.

Item Type:	Refereed Article
Research Division:	Chemical Sciences
Research Group:	Inorganic Chemistry
Research Field:	Transition Metal Chemistry
Objective Division:	Expanding Knowledge
Objective Group:	Expanding Knowledge
Objective Field:	Expanding Knowledge in the Chemical Sciences
UTAS Author:	Brookes, NJ (Dr Nigel Brookes)
UTAS Author:	Ariafard, A (Associate Professor Alireza Ariafard)
UTAS Author:	Yates, BF (Professor Brian Yates)
ID Code:	62469
Year Published:	2009
Funding Support:	Australian Research Council (DP0986529)
Web of Science® Times Cited:	36
Deposited By:	Chemistry
Deposited On:	2010-03-12
Last Modified:	2010-04-12
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