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<p>Germavinylidenes (R<sub>2</sub>C=Ge), the heavier congeners of vinylidenes, have long remained elusive, both as free species and in Lewis base-stabilized forms. Herein, we report the isolation of a base-stabilized germavinylidene employing an imine-functionalized cyclic (alkyl)(amino)carbene (imino-CAAC) ligand. Comprehensive structural characterization, supported by theoretical calculations, confirms the presence of a Ge=C double bond, with the divalent germanium center coordinated by the imine donor. Preliminary reactivity studies reveal a rich chemical profile: the complex undergoes selective methylation at the germanium center, forms a π-dominated coordination complex with iron carbonyl, and acts as a germanium atom transfer reagent to generate a rare tetraazagermylene. Furthermore, a [2 + 2] cycloaddition with isocyanate provides compelling evidence for the Ge=C double bond character. These results underscore the previously unexplored potential of imino-CAAC ligands in stabilizing reactive and uncharted p-block main group species.</p>

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A base-stabilized germavinylidene

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年11月14日

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  • Bin Li,
  • Jiancheng Li,
  • Yanling Zhu,
  • Jicheng Wang,
  • Yuanyuan Wang,
  • Manbo Zhang,
  • Liu Leo Liu

摘要

Germavinylidenes (R2C=Ge), the heavier congeners of vinylidenes, have long remained elusive, both as free species and in Lewis base-stabilized forms. Herein, we report the isolation of a base-stabilized germavinylidene employing an imine-functionalized cyclic (alkyl)(amino)carbene (imino-CAAC) ligand. Comprehensive structural characterization, supported by theoretical calculations, confirms the presence of a Ge=C double bond, with the divalent germanium center coordinated by the imine donor. Preliminary reactivity studies reveal a rich chemical profile: the complex undergoes selective methylation at the germanium center, forms a π-dominated coordination complex with iron carbonyl, and acts as a germanium atom transfer reagent to generate a rare tetraazagermylene. Furthermore, a [2 + 2] cycloaddition with isocyanate provides compelling evidence for the Ge=C double bond character. These results underscore the previously unexplored potential of imino-CAAC ligands in stabilizing reactive and uncharted p-block main group species.