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Factors dictating carbene formation at (PNP)Ir

Brookes, Nigel J; Whited, Matthew; Ariafard, Alireza; Stranger, Robert; Grubbs, Robert; Yates, Brian F

Description

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...[Show more]

dc.contributor.authorBrookes, Nigel J
dc.contributor.authorWhited, Matthew
dc.contributor.authorAriafard, Alireza
dc.contributor.authorStranger, Robert
dc.contributor.authorGrubbs, Robert
dc.contributor.authorYates, Brian F
dc.date.accessioned2015-12-10T22:57:59Z
dc.identifier.issn0276-7333
dc.identifier.urihttp://hdl.handle.net/1885/60659
dc.description.abstractThe 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.
dc.publisherAmerican Chemical Society
dc.sourceOrganometallics
dc.subjectKeywords: Back-donation; C-h activation; Carbene ligands; Carbenes; Cyclic ether; D electrons; Density functionals; Intermediate specie; Mechanistic analysis; Reaction directions; Steric hindrances; Vinyl ethers; Activation analysis; Density functional theory; Ethe
dc.titleFactors dictating carbene formation at (PNP)Ir
dc.typeJournal article
local.description.notesImported from ARIES
local.identifier.citationvolume29
dc.date.issued2010
local.identifier.absfor030701 - Quantum Chemistry
local.identifier.ariespublicationu4217927xPUB554
local.type.statusPublished Version
local.contributor.affiliationBrookes, Nigel J, University of Tasmania
local.contributor.affiliationWhited, Matthew, California Institute of Technology
local.contributor.affiliationAriafard, Alireza, Islamic Azad University
local.contributor.affiliationStranger, Robert, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationGrubbs, Robert, California Institute of Technology
local.contributor.affiliationYates, Brian F, University of Tasmania
local.description.embargo2037-12-31
local.bibliographicCitation.issue19
local.bibliographicCitation.startpage4239
local.bibliographicCitation.lastpage4250
local.identifier.doi10.1021/om100211a
local.identifier.absseo970103 - Expanding Knowledge in the Chemical Sciences
dc.date.updated2016-02-24T10:44:12Z
local.identifier.scopusID2-s2.0-77957678983
local.identifier.thomsonID000282303300007
CollectionsANU Research Publications

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