TY - JOUR
T1 - Dichotomy of Delocalization/Localization and Charge-Shift Bonding in Germanazene and its Heavier Group 14 Analogues
T2 - a Valence Bond Study
AU - Jain, Shailja
AU - Danovich, David
AU - Radenković, Slavko
AU - Shaik, Sason
N1 - Publisher Copyright:
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
PY - 2023/6/27
Y1 - 2023/6/27
N2 - 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).
AB - 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).
KW - aromaticity
KW - charge shift bond ⋅germanazene
KW - resonance energy
KW - valence bond theory
UR - http://www.scopus.com/inward/record.url?scp=85156163631&partnerID=8YFLogxK
U2 - 10.1002/chem.202300992
DO - 10.1002/chem.202300992
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C2 - 37073808
AN - SCOPUS:85156163631
SN - 0947-6539
VL - 29
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 36
M1 - e202300992
ER -