Work

sp-Hybridized Seesaw Ge0 Complexes via Germylone-to-Seesaw Isomerization in a Four-Electron Cyclic N2Ge2 Ligand

Year: 2025

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide We report the first examples of two linear trigermanium complexes (μ-Ge)(κ 2 - N 2 Ge 2 Ar ) (Ar = 2,4,6-Me 3 C 6 H 2 ( 4 ), 2,6-Et 2 C 6 H 3 ( 5 )), in which each central Ge 0 atom displays a seesaw geometry enforced by a four-electron cyclic N 2 Ge 2 Ar ligand. The pyridine-stabilized sp-hybridized Ge 0 center is a four-electron donor and two terminal germylenes are electron-acceptors. Comparative studies show that the N 2 Ge 2 scaffold uniquely stabilizes the Ge 0 atom. This work not only introduces a new class of main-group seesaw complexes but also demonstrates ligand-driven control over hybridization and donor–acceptor dynamics. Compound 5 underwent one-electron reduction, followed by ligand rearrangement and dimerization, to afford a novel hexanuclear homounivalent germanium cluster, 10, featuring a snake-like Ge 6 core. In 10, each Ge atom in the central Ge I –Ge I unit is solely stabilized one amido ligand, while each of the remaining four Ge atoms is supported by one amido and one pyridyl donor. The isolation of a bulkier analogue ( 11 ) and a heteronuclear Ge 4 Sn 2 cluster ( 16 ) further underscores the crucial role of ligand sterics in stabilizing these assemblies. These findings expand the structural diversity of low-valent group 14 compounds and establish a new paradigm for constructing multinuclear tetrel clusters.

Source: Inorganic Chemistry

DOI: 10.1021/acs.inorgchem.5c02120