Cleavage of carbon dioxide by an iridium-supported Fischer carbene. A DFT investigation

Nigel J. Brookes; Alireza Ariafard; Robert Stranger; Brian F. Yates

doi:10.1021/ja809320x

Cleavage of carbon dioxide by an iridium-supported Fischer carbene. A DFT investigation

Nigel J. Brookes, Alireza Ariafard, Robert Stranger, Brian F. Yates

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Abstract

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.

Original language	English
Pages (from-to)	5800-5808
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	131
Issue number	16
DOIs	https://doi.org/10.1021/ja809320x
Publication status	Published - 29 Apr 2009

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abstract = "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.",

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AU - Brookes, Nigel J.

AU - Ariafard, Alireza

AU - Stranger, Robert

AU - Yates, Brian F.

PY - 2009/4/29

Y1 - 2009/4/29

N2 - 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.

AB - 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.

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 16

ER -

Cleavage of carbon dioxide by an iridium-supported Fischer carbene. A DFT investigation

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