Synthesis and One-Electron Reduction of Donor-Acceptor-Stabilized Si^II-E^II-Si^II Trimetallylenes (E = Ge, Sn, Pb).

Authors

Chaopeng Hu, Shenglai Yao, Christian Lorent, Matthias Driess

Published in

Angewandte Chemie (International ed. in English). Pages e6871080. Jul 03, 2026. Epub Jul 03, 2026.

Abstract

Herein, we report isolable donor-acceptor-stabilized Si^II-E^II-Si^II trimetallylenes (E = Ge (2), Sn (3), Pb (4); Si^II = Mes(cAAC)Si; Mes = 2,4,6-Me₃C₆H₂; cAAC = C(CH₂)(CMe₂)₂N-2,6-ⁱPr₂C₆H₃), stabilized by a cyclic alkylaminocarbene attached to the divalent Si atoms. They were synthesized through salt-metathesis reactions of the dimeric silanylidene anion (Si^IIK)₂ 1a and EX₂ precursors (X = Cl, N(SiMe₃)₂). Computational analyses reveal that 2-4 adopt bent donor-acceptor-stabilized Si^II-E^II-Si^II frameworks featuring polarized Si-C(cAAC) π interactions together with delocalized Si-E π interactions involving the Lewis-acidic E^II center. This donor-acceptor electronic structure results in small HOMO-LUMO gaps, giving rise to pronounced near-infrared (NIR) absorption. Remarkably, the one-electron reduction of 2 and 3 leads to the Ge^I- and Sn^I- radical anions 2^•- and 3^•-, respectively, thereby highlighting that this donor-acceptor motif can even stabilize heavy Group 14 elements in lower oxidation states.

PMID:
42397857
Bibliographic data and abstract were imported from PubMed on 04 Jul 2026.

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