Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, People's Republic of China.
Inorg Chem. 2013 Aug 19;52(16):9479-86. doi: 10.1021/ic4011345. Epub 2013 Aug 8.
Metalation of the (iminophosphoranyl)phosphine PPh2CH2(PPh2═NSiMe3) (1) with an equimolar amount of n-BuLi afforded the monolithium salt [Li{CH(PPh2)(PPh2═NSiMe3)}(THF)2] (2). The reaction of 2 with GeCl2·1,4-dioxane has led to the formation of a germavinylene moiety, which trimerized to form a new heterocyclic cage compound, [{(PPh2═NSiMe3)(PPh2)C═Ge:}{(PPh2═NSiMe3)(PPh2)C}2Ge→Ge:] (3). A similar reaction of the lithium methanide complex 2 with SnCl2 afforded the stannavinylidene moiety, which underwent a "head-to-tail" cycloaddition to form a stable 1,3-distannacyclobutane, 4. A trapping reaction of 4 with diiron nonacarbonyl gave the novel iron stannavinylidene complex 5. The solid-state structure analysis of 5 reveals that it contains two stannavinylidene moieties bonded in a Sn-P "head-to-tail" fashion, with one of the tin(II) centers coordinating to a Fe(CO)4 moiety. The X-ray structures of 2-5 have been determined by X-ray crystallography. In addition, the dynamic behavior of 5 has been studied by means of variable-temperature (31)P and (119)Sn NMR spectroscopy.
用等摩尔的 n-BuLi 对 (iminophosphoranyl)膦 PPh2CH2(PPh2═NSiMe3)（1）进行金属化，得到单锂盐 [Li{CH(PPh2)(PPh2═NSiMe3)}(THF)2]（2）。2 与 GeCl2·1,4-二恶烷的反应导致形成了一个锗甲炔基部分，该部分三聚化形成了一种新的杂环笼状化合物，[{(PPh2═NSiMe3)(PPh2)C═Ge:}{(PPh2═NSiMe3)(PPh2)C}2Ge→Ge:]（3）。2 与 SnCl2 的类似锂甲烷化物复合物的反应得到了锡甲炔基部分，该部分经历了“头到尾”环加成反应，形成了稳定的 1,3-二锡环丁烷，4。4 与二铁九羰基的捕获反应得到了新型铁锡甲炔基配合物 5。5 的固态结构分析表明，它含有两个以 Sn-P“头到尾”方式键合的锡甲炔基部分，其中一个锡（II）中心与 Fe(CO)4 部分配位。2-5 的 X 射线结构已通过 X 射线晶体学确定。此外，还通过变温（31）P 和（119）Sn NMR 光谱研究了 5 的动态行为。
