Aromaticity of some carbenes and their heavier analogs in light of gauge‐including magnetically induced current approach as a new magnetic criterium

Abstract

The computational method of gauge‐including magnetically induced current (GIMIC) was used at B3LYP/Def2‐TZVP level to test aromaticity of a series of carbenes and their heavier analogs. These were unsaturated N‐heterocyclic Arduengo‐type compounds 1 and their benzannulated analogs 2, as well as silylene and germylene 3. The magnitudes of induced current (IC) for various bonds were calculated and the isosurfaces of signed modulus of IC density were presented visually. The results obtained have demonstrated applicability of the GIMIC method to the 14th group carbene analogs studied as they confirm aromaticity of type 1 and 2 molecules and π‐conjugated but not aromatic nature of molecules 3 that was established previously using other aromaticity criteria. A nontrivial conclusion that germylenes of types 1 and 2 are more aromatic than silylenes is reinforced.

Aromaticity Suppression by Intermolecular Coordination. Optical Spectra and Electronic Structure of Heavy Carbene Analogues with an Amidophenolate Backbone

“…We have already applied this approach to type I and II molecules. 38 The results have demonstrated the applicability of the GIMIC method to the carbene analogues containing a group 14 atom in the cycle. The data obtained by this method for model monomeric type III molecules with an H substituent at nitrogen atom, H APEs 1″−3″, are presented in Figure 7 and Table 5.…”

“…We have already applied this approach to type I and II molecules . The results have demonstrated the applicability of the GIMIC method to the carbene analogues containing a group 14 atom in the cycle.…”

“…38 The IC strength values given in Table 5 for the monomeric type III molecules are similar to those obtained for the type II molecules. 38…”

Aromaticity of 1-Heterocyclopropenes Containing an Atom of Group 14 or 4

“…The presence of σ aromaticity evidenced for the organic cycles C 3 H 6 and C 3 H 4 agrees well with NICS in–out data (see above). Recently we have studied by the GIMIC technique some carbenes and their heavier analogues . In this work we apply this approach to the HCPs in question.…”

“…Recently we have studied by the GIMIC technique some carbenes and their heavier analogues. 91 In this work we apply this approach to the HCPs in question. To visualize the IC of 1Si H and 1Ge H , the IC modulus surfaces were built up; the results (designated as Jmod plots) are presented in Figure 7.…”