Evans Matthew J, Burke Finlay M, Chapple Peter M, Fulton J Robin
School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600, Wellington 6012, New Zealand.
Inorg Chem. 2021 Jun 7;60(11):8293-8303. doi: 10.1021/acs.inorgchem.1c00971. Epub 2021 May 14.
We report the synthesis of aromatic germanimines [(HMDS)Ge═NAr] (Ar = Ph, Mes, Dipp; Mes = 2,4,6-MeCH, Dipp = 2,6-PrCH) and an investigation into their associated reactivity. [(HMDS)Ge═NPh] decomposes above -30 °C, while [(HMDS)Ge═NDipp] engages in an intramolecular reaction at 60 °C. [(HMDS)Ge═NMes] was shown to rearrange via a 1,3-silyl migration to give [(HMDS){(SiMe)(Mes)N}Ge(NSiMe)] in a 1:7 equilibrium mixture at room temperature. These latter germanimines react with unsaturated polar substrates such as CO, ketones, and arylisocyanate via a [2 + 2] cycloaddition pathway.
我们报道了芳香族锗亚胺[(HMDS)Ge═NAr]（Ar = Ph、Mes、Dipp；Mes = 2,4,6-MeCH，Dipp = 2,6-PrCH）的合成及其相关反应性的研究。[(HMDS)Ge═NPh]在高于-30°C时分解，而[(HMDS)Ge═NDipp]在60°C时发生分子内反应。[(HMDS)Ge═NMes]被证明通过1,3-硅基迁移重排，在室温下以1:7的平衡混合物形式生成[(HMDS){(SiMe)(Mes)N}Ge(NSiMe)]。这些锗亚胺通过[2 + 2]环加成途径与不饱和极性底物如CO、酮和芳基异氰酸酯反应。
