Dichotomy of Delocalization/Localization and Charge-Shift Bonding in Germanazene and its Heavier Group 14 Analogues: a Valence Bond Study

Shailja Jain, David Danovich, Slavko Radenković*, Sason Shaik*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

We present here a valence bond analysis of structure and π-delocalization in Ge3(NH)3, which models germanazene that was prepared by Power et al. To get a broader perspective, we explore the entire E3(NH)3 series (E=C, Si, Ge, Sn, Pb). Thus, while (4n+2)π systems of carbon rings are aromatic with cyclic π-delocalization, the E3(NH)3 rings are dominated by a nonbonded structure, wherein π-lone pairs are localized on the N atoms. Nevertheless, these molecules enjoy large covalent-ionic resonance energies of 153.0, 86.6, 74.2, 61.2, and 58.9 kcal/mol, respectively, for E=C, Si, Ge, Sn, Pb. The covalent-ionic mixing in E3(NH)3 creates π-systems, which are stabilized by charge-shift bonding. Thus, unlike in benzene, in Ge3(NH)3 delocalization of π-electron pairs of the N atoms is primarily confined to the domains of their adjacent Ge atoms. These features carry over to the substituted germanazene, Ge3(NAr)3 (Ar=Ph).

Original languageEnglish
Article numbere202300992
JournalChemistry - A European Journal
Volume29
Issue number36
DOIs
StatePublished - 27 Jun 2023

Bibliographical note

Publisher Copyright:
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Keywords

  • aromaticity
  • charge shift bond ⋅germanazene
  • resonance energy
  • valence bond theory

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