Theoretical Investigation of Hydride Insertion into N-Heterocyclic Carbenes Containing N, P, C, O and S Heteroatoms
journal contributionposted on 03.05.2021, 02:27 by Khalidah HM Al Furaiji, Kalon J Iversen, Jason Dutton, David Wilson
The 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.
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.
JournalChemistry - An Asian Journal
Pagination9p. (p. 3745-3752)
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Science & TechnologyPhysical SciencesChemistry, MultidisciplinaryChemistrydensity functional calculationsDFThydride insertionN-heterocyclic carbenesreaction mechanismsGAUSSIAN-BASIS SETSRING-EXPANSIONELECTRONIC-STRUCTURECORRELATION-ENERGYLIGAND PROPERTIESBOND-CLEAVAGEATOMS LIADDUCTSMECHANISMCATALYSTSGeneral Chemistry