Premium
Tuning the π‐Accepting Properties of Mesoionic Carbenes: A Combined Computational and Experimental Study
Author(s) -
Dong Zhaowen,
Blaskovits J. Terence,
FadaeiTirani Farzaneh,
Scopelliti Rosario,
Sienkiewicz Andrzej,
Corminboeuf Clémence,
Severin Kay
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101742
Subject(s) - mesoionic , carbene , substituent , chemistry , ligand (biochemistry) , aryl , context (archaeology) , computational chemistry , acceptor , combinatorial chemistry , photochemistry , stereochemistry , medicinal chemistry , organic chemistry , catalysis , physics , paleontology , biochemistry , alkyl , receptor , biology , condensed matter physics
Mesoionic imidazolylidenes are recognized as excellent electron‐donating ligands in organometallic and main group chemistry. However, these carbene ligands typically show poor π‐accepting properties. A computational analysis of 71 mesoionic imidazolylidenes that bear different aryl or heteroaryl substituents in C2 position was performed. The study has revealed that a diphenyltriazinyl (Dpt) substituent renders the corresponding carbene particularly π‐acidic. The computational results could be corroborated experimentally. A mesoionic imidazolylidene with a Dpt substituent was found to be a better σ‐donor and a better π‐acceptor compared to an Arduengo‐type N‐heterocyclic carbene. To demonstrate the utility of the new carbene, the ligand was used to stabilize a low‐valent paramagnetic tin compound.