Ring-opening addition of hydrogen chloride to monocyclic and spirocyclic [1]ferrocenophanes: a convenient and controlled route to ferrocenylchlorosilanes and germanes
Ring-opening addition of hydrogen chloride to monocyclic and spirocyclic [1]ferrocenophanes: a convenient and controlled route to ferrocenylchlorosilanes and germanes
复制标题
氯化氢开环加成至单环和螺环[1]二茂铁：一种便捷且受控的二茂铁基氯硅烷和锗烷路线
DOI：
10.1039/a806682e
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发表时间：
1998
期刊：
影响因子：
--
通讯作者：
I. Manners
中科院分区：
文献类型：
--
作者：
M. MacLachlan;M. Ginzburg;Juan Zheng;Oliver Knöll;A. Lough;I. Manners
HCl开环加成[1]二茂铁并吡喃提供了一种制备氯硅烷和含二茂铁基取代基的锗烷的通用方法。用盐酸与二甲基[1]硅二茂铁烷fcSiMe 2（1a）[fc=Fe（η-C5 H4）2]反应，得到氯二甲基二茂铁基硅烷FcMe 2SiCl（3a）[Fc=（η-C5 H4）Fe（η-C5 H5）]，产率68%。三氯二茂铁基硅烷，FcSiCl 3（3b），和氯二甲基二茂铁基锗烷，FcMe 2GeCl（3c），通过类似的路线从二茂铁甲烷fcSiCl 2（1b）和fcGeMe 2（1c）制备。将HCl开环加成到螺环[1]二茂铁烷fcSi（CH 2）3（4）上，导致应变二茂铁烷的Si-C键断裂，以84%的产率得到硅杂环丁烷FcSiCl（CH 2）3（5）。此外，用HCl处理螺环[1]硅二茂铁烷fc_2Si（6）得到二氯二二茂铁基硅烷的橙子晶体，Fc_2SiCl_2（7），产率为88%。在三乙胺存在下水解7生成双二茂铁基硅烷二醇，Fc 2Si（OH）2（8），产率90%。单晶X-射线衍射研究结合光谱鉴定证实，8结晶在一个新的珠和链的主题。
The ring-opening addition of HCl to [1]ferrocenophanes has been shown to provide a general method for the preparation of chlorosilanes and germanes with ferrocenyl substituents. Reaction of HCl with dimethyl[1]silaferrocenophane, fcSiMe2 (1a) [fc=Fe(η-C5H4)2], affords chlorodimethylferrocenylsilane, FcMe2SiCl (3a) [Fc=(η-C5H4)Fe(η-C5H5)], in 68% yield. Trichloroferrocenylsilane, FcSiCl3 (3b), and chlorodimethylferrocenylgermane, FcMe2GeCl (3c), were prepared by an analogous route from ferrocenophanes fcSiCl2 (1b) and fcGeMe2 (1c). Ring-opening addition of HCl to the spirocyclic [1]ferrocenophane, fcSi(CH2)3 (4), leads to cleavage of the Si–C bond of the strained ferrocenophane, giving the silacyclobutane FcSiCl(CH2)3 (5) in 84% yield. Moreover, treatment of the spirocyclic [1]silaferrocenophane fc2Si (6) with HCl affords orange crystals of dichlorodiferrocenylsilane, Fc2SiCl2 (7), in 88% yield. Hydrolysis of 7 in the presence of triethylamine generated diferrocenylsilanediol, Fc2Si(OH)2 (8), in 90% yield. A single crystal X-ray diffraction study combined with spectroscopic identification confirmed that 8 crystallizes in a new bead-and-chain motif.