Gendy Chris, Mikko Rautiainen J, Mailman Aaron, Tuononen Heikki M
Department of Chemistry, NanoScience Centre, University of Jyväskylä, P.O. Box. 35, 40014, Jyväskylä, Finland.
Chemistry. 2021 Oct 19;27(58):14405-14409. doi: 10.1002/chem.202102804. Epub 2021 Sep 15.
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 π-electrons capable of binding even weak electrophiles. The germanylidene anions reacted with CO to give μ-CO -κC:κO 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.
通过环状（烷基）（氨基）卡宾和超甲硅烷基配体支撑的稀有单核和螺旋链低价锗亚烷基阴离子，是通过从相应的亚锗烯前体经稳定且可分离的锗自由基逐步还原而合成的。这些阴离子的电子结构可用亚烷基和亚烷基酮共振形式来描述，其中锗-碳π电子甚至能够与弱亲电试剂结合。锗亚烷基阴离子与一氧化碳反应生成μ-CO-κC:κO配合物，这是低价锗的一种罕见配位模式，而相关的中性锗酮无法形成这种模式。这些结果表明低价锗亚烷基阴离子是用于小分子活化的高效单中心亲核试剂。
