期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 27, 期 58, 页码 14405-14409出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202102804
关键词
donor-acceptor systems; germanium; main group elements; small molecule activation; sub-valent compounds
资金
- University of Jyvaskyla
- European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme [772510]
- European Research Council (ERC) [772510] Funding Source: European Research Council (ERC)
Rare mononuclear and helical chain low-valent germanylidene anions, synthesized by stepwise reduction from corresponding germylene precursors, exhibit electronic structures describable with ylidene and ylidone resonance forms, and act as efficient single-site nucleophiles for activating small molecules.
Rare mononuclear and helical chain low-valent germanylidene anions supported by cyclic (alkyl)(amino)carbene and hypermetallyl ligands were synthesised by stepwise reduction from corresponding germylene precursors via stable and isolable germanium radicals. The electronic structures of the anions can be described with ylidene and ylidone resonance forms with the Ge-C pi-electrons capable of binding even weak electrophiles. The germanylidene anions reacted with CO2 to give mu-CO2-kappa C:kappa O complexes, a rare coordination mode for low-valent germanium and inaccessible for the related neutral germylones. These results implicate low-valent germanylidene anions as efficient single-site nucleophiles for activation of small molecules.
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