Aromaticity of 1-Heterocyclopropenes Containing an Atom of Group 14 or 4статья
Статья опубликована в высокорейтинговом журнале
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Дата последнего поиска статьи во внешних источниках: 24 сентября 2020 г.
Аннотация:The aromaticity of three-membered monoheterocycles containing a group 14 or 4 element was investigated by using modern aromaticity criteria: structural, electronic (FBO), optical (vibrational spectroscopy), energetic (ISE), and magnetic (NICS-scan, GIMIC). The results of all methods used show that the group 14 compounds are aromatic, with cyclopropene exhibiting σ aromaticity, whereas sila- and germacyclopropenes X2EC2R2 exhibit pseudo-π aromaticity due to the interaction of the C═C π bond orbital with the low-lying vacant antibonding σ* orbital of the X2E fragment (E = Si, Ge). At the same time, the results of MO and magnetic descriptor calculations testify against the aromaticity of group 4 cyclopropenes Cp2MC2R2 (M = Ti, Zr, Hf). Thus, a fundamental dissimilarity in bonding schemes and electronic structure was disclosed between 1-heterocyclopropenes containing E = C, Si, Ge atoms and those containing M = Ti, Zr, Hf atoms, the latter molecules being in essence π complexes of acetylene.