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Factors Dictating Carbene Formation at (PNP)Ir

Brookes, Nigel J. and Whited, Matthew T. and Ariafard, Alireza and Stranger, Robert and Grubbs, Robert H. and Yates, Brian F. (2010) Factors Dictating Carbene Formation at (PNP)Ir. Organometallics, 29 (19). pp. 4239-4250. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20101022-082918964

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Abstract

The mechanistic subtleties involved with the interaction of an amido/bis(phosphine)-supported (PNP)Ir fragment with a series of linear and cyclic ethers have been investigated using density functional theory. Our analysis has revealed the factors dictating reaction direction toward either an iridium-supported carbene or a vinyl ether adduct. The (PNP)Ir structure will allow carbene formation only from accessible carbons α to the ethereal oxygen, such that d electron back-donation from the metal to the carbene ligand is possible. Should these conditions be unavailable, the main competing pathway to form vinyl ether can occur, but only if the (PNP)Ir framework does not sterically interfere with the reacting ether. In situations where steric hindrance prevents unimpeded access to both pathways, the reaction may progress to the initial C−H activation but no further. Our mechanistic analysis is density functional independent and whenever possible confirmed experimentally by trapping intermediate species experimentally. We have also highlighted an interesting systematic error present in the DFT analysis of reactions where steric environment alters considerably within a reaction.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/om100211aDOIArticle
http://pubs.acs.org/doi/abs/10.1021/om100211aPublisherArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2010 American Chemical Society. Received March 18, 2010. Publication Date (Web): September 7, 2010. We thank the Australian Research Council (ARC), BP (MC2 program), and the Moore Foundation (fellowship to M.T.W.) for project funding. We are also indebted to the National Computational Infrastructure (NCI) and the Tasmanian Partnership for Advanced Computing (TPAC).
Funders:
Funding AgencyGrant Number
Australian Research CouncilUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
BP MC2 programUNSPECIFIED
Issue or Number:19
Record Number:CaltechAUTHORS:20101022-082918964
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20101022-082918964
Official Citation:Factors Dictating Carbene Formation at (PNP)Ir Nigel J. Brookes, Matthew T. Whited, Alireza Ariafard, Robert Stranger, Robert H. Grubbs, Brian F. Yates Organometallics 2010 29 (19), 4239-4250
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:20475
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:30 Nov 2010 22:29
Last Modified:03 Oct 2019 02:10

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