Is the term 'Carbene' justified for remote N-heterocyclic carbenes (r-NHCs) and abnormal N-heterocyclic carbenes (aNHCs/MICs)?

摘要

The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of typical N-heterocyclic carbenes NHCs, r-NHCs, a-NHCs and MICs have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. Prior to that both structures and C-13 chemical shifts were calculated and in case of isolated carbenes the computed delta(C-13)/ppm values compared (as a quality criterion for obtained structures) with the experimental ones. The TSNMRS values of the studied carbenes, which are in mesomeric equilibrium with zwitterionic (ylide/betaine/mesoionic) resonance contributors, are employed to qualify and quantify the present electronic structure and if the term carbene is still justified to denote the compounds studied. The results, thus obtained from spatial magnetic properties (TSNMRS), are compared with the geometry of the compounds, the corresponding WIBERG's bond index values, and the C-13 chemical shifts especially of the carbene electron-deficient centre. (C) 2019 Elsevier Ltd. All rights reserved.