Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, Singapore 637371.
Chemistry. 2012 Feb 27;18(9):2685-91. doi: 10.1002/chem.201102201. Epub 2012 Jan 24.
The synthesis and characterization of new amidinate-stabilized germatrisilacyclobutadiene ylides [L(3)Si(3)GeL'] (L=PhC(NtBu)(2); L'=ËL; Ë=Ge (3), Si (7)) are described. Compound 3 was prepared by the reaction of [LSi-SiL] (1) with one equivalent of [LGe-GeL] (2) in THF. Compound 7 was synthesized by the reaction of 2 with excess 1 in THF. The bisamidinate germylene [L(2)Ge:] (4) is a by-product in both reactions. Moreover, compound 7 was prepared by the reaction of 3 with one equivalent of 1 in THF. Compounds 3 and 7 have been characterized by NMR spectroscopy, X-ray crystallography, and theoretical studies. The results show that compounds 3 and 7 are not antiaromatic. The puckered Si(3) Ge four-membered rings in 3 and 7 have a ylide structure, which is stabilized by amidinate ligands and the electron delocalization within the Si(3) Ge four-membered ring.
新型酰胺稳定的锗杂硅环丁二烯亚基化物 [L(3)Si(3)GeL'](L=PhC(NtBu)(2);L'=ËL;Ë=Ge(3),Si(7))的合成与表征。化合物 3 通过[LSi-SiL](1)与[LGe-GeL](2)的 1 当量反应在 THF 中制备。化合物 7 通过 2 与过量 1 在 THF 中的反应合成。双酰胺基锗亚基 [L(2)Ge:](4)是两个反应的副产物。此外,化合物 7 通过 3 与 1 的 1 当量在 THF 中的反应制备。化合物 3 和 7 通过 NMR 光谱、X 射线晶体学和理论研究进行了表征。结果表明,化合物 3 和 7 不是反芳香性的。3 和 7 中的翘曲 Si(3) Ge 四元环具有亚基结构,由酰胺基配体和 Si(3) Ge 四元环内的电子离域稳定。