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Insertion of Group 12-16 Hydrides into NHCs_AAM.pdf (421.76 kB)

Theoretical Investigation of Hydride Insertion into N-Heterocyclic Carbenes Containing N, P, C, O and S Heteroatoms

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Version 2 2021-05-03, 02:27
Version 1 2021-04-30, 03:48
journal contribution
posted on 2021-05-03, 02:27 authored by Khalidah HM Al Furaiji, Kalon J Iversen, Jason DuttonJason Dutton, David WilsonDavid 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.


Publication Date



Chemistry - An Asian Journal






9p. (p. 3745-3752)





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