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- Title
Dichotomy of Delocalization/Localization and Charge‐Shift Bonding in Germanazene and its Heavier Group 14 Analogues: a Valence Bond Study.
- Authors
Jain, Shailja; Danovich, David; Radenković, Slavko; Shaik, Sason
- 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).
- Subjects
VALENCE bonds; DELOCALIZATION energy; ATOMS; TIN; MOLECULES
- Publication
Chemistry - A European Journal, 2023, Vol 29, Issue 36, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202300992