Insertion of Group 12-16 Hydrides into NHCs_AAM.pdf (421.76 kB)
Download fileTheoretical Investigation of Hydride Insertion into N-Heterocyclic Carbenes Containing N, P, C, O and S Heteroatoms
journal contribution
posted on 2021-05-03, 02:27 authored by Khalidah HM Al Furaiji, Kalon J Iversen, Jason DuttonJason Dutton, David WilsonDavid WilsonThe endocyclic ring expansion of N-heterocyclic carbene (NHC) rings containing one N atom and one P, N, C, O or S heteroatom has been investigated in a computational study. Ring expansion was determined to follow a common pathway, leading to a final expanded six-membered ring that was predicted to be thermodynamically stable for all heterocycles. However, reactivity is driven by kinetics with ring-expansion reactivity not expected for the P/NHC and C/NHC (cAAC) containing heterocycles due to large barriers for ring-expansion. In contrast, ring expansion is predicted to be feasible for N-heterocyclic carbenes containing an O (O/NHC) or S (S/NHC) heteroatom, with insertion into the O−C and S−C bond favoured over insertion into the N−C bond, respectively.
Funding
This work was generously supported by The Australian Research Council (JLD; FT160100007) and La Trobe University. We thank La Trobe University, NCI and Intersect for computing resources.
History
Publication Date
2018-01-01Journal
Chemistry - An Asian JournalVolume
13Issue
23Pagination
9p. (p. 3745-3752)Publisher
WileyISSN
1861-4728Rights Statement
The Author reserves all moral rights over the deposited text and must be credited if any re-use occurs. Documents deposited in OPAL are the Open Access versions of outputs published elsewhere. Changes resulting from the publishing process may therefore not be reflected in this document. The final published version may be obtained via the publisher’s DOI. Please note that additional copyright and access restrictions may apply to the published version.Publisher DOI
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Keywords
Science & TechnologyPhysical SciencesChemistry, MultidisciplinaryChemistrydensity functional calculationsDFThydride insertionN-heterocyclic carbenesreaction mechanismsGAUSSIAN-BASIS SETSRING-EXPANSIONELECTRONIC-STRUCTURECORRELATION-ENERGYLIGAND PROPERTIESBOND-CLEAVAGEATOMS LIADDUCTSMECHANISMCATALYSTSGeneral Chemistry