366491-22-7Relevant academic research and scientific papers
Steric Properties of N-Heterocyclic Carbenes affect the Performance of Electronic Probes
Barnett, Christopher,Cole, Marcus L.,Harper, Jason B.
supporting information, p. 4954 - 4958 (2021/12/02)
Electronic probes of ligands, particularly carbenes, are widely used in assessing electronic properties; the results inform the selection of a ligand for a given application. As such, it is important to ensure the data obtained is reliable and unaffected by other factors, such as the steric bulk of the ligand. The effects of such steric factors on two commonly used electronic probes (based on palladium and selenium) are investigated here, with the selenium adduct found to be particularly sensitive. It is hoped that this serves as a cautionary tale to always critically evaluate what a probe is measuring.
Elimination of Ethene from 1,2-Diiodoethane Induced by N-Heterocyclic Carbene Halogen Bonding
Poynder, Tiffany B.,Savaliya, Dharmeshkumar P.,Molino, Andrew,Wilson, David J. D.,Dutton, Jason L.
, p. 614 - 619 (2019/07/31)
The attempted synthesis of N-heterocyclic carbene (NHC)-stabilised dicarbon (C2) fragments via nucleophilic substitution at 1,2-diiodoethane is reported. Rather than the expected SN2 pathway, clean elimination of ethene and formation of an iodoimidazolium cation was observed. The resistance towards nucleophilic substitution piqued interest, and subsequent investigation determined NHC-halogen bonding as the source. This is in contrast to reactions between NHCs and other alkyl halides, where substitution or elimination pathways are reported. A detailed theoretical study between these cases highlights the importance of iodine as a halogen bond donor compared with other halogens, and shows that NHCs are excellent halogen bond acceptors. This reactivity suggests potential for application of the halogen bonding interaction between NHCs and organic compounds.
