Synthesis, structure, and reactivity of trisilanes containing the 8-(dimethylamino)-1-naphthyl group at the central silicon atom. A novel nickel- or palladium-catalyzed degradation of trisilane to disilane and silylene species
Synthesis, structure, and reactivity of trisilanes containing the 8-(dimethylamino)-1-naphthyl group at the central silicon atom. A novel nickel- or palladium-catalyzed degradation of trisilane to disilane and silylene species
复制标题
中心硅原子含有 8-(二甲基氨基)-1-萘基的丙硅烷的合成、结构和反应性。
DOI：
10.1021/om00028a028
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发表时间：
1993
期刊：
影响因子：
2.8
通讯作者：
Y. Ito*
中科院分区：
文献类型：
--
作者：
K. Tamao;Yoshihiro Tarao;Y. Nakagawa;K. Nagata;Y. Ito*
合成了三种中心硅原子上含8-二甲氨基-1-萘基的三硅烷。虽然X射线结构分析和NMR研究表明，丙硅烷骨架是相当不情愿的五配位，不寻常的紫外和质谱特征和高反应性对镍和钯催化剂已被确认。在Ni和Pd催化的反应中，丙硅烷中的两端硅原子相互偶联形成相应的乙硅烷。在Pd的情况下，作为反应性亚甲硅烷基物质挤出的中心硅原子被二苯基乙炔捕获，在色谱处理后形成4-氧杂-3，5-二硅杂环戊-1-烯衍生物的顺式/反式混合物。反式异构体的X-射线结构表明存在两个轻微的五配位硅原子。
Three trisilanes containing the 8-(dimethylamino)-l-naphthyl group on the central silicon atom have been prepared. While X-ray structural analysis and NMR studies reveal that the trisilane skeleton is rather reluctant to pentacoordination, unusual UV and mass spectral features and high reactivity toward á nickel and a palladium catalyst have been recognized. In the Ni-and Pd-catalyzed reactions, the twoterminal silicon atoms in the trisilane couple each other to form the corresponding disilane. The central silicon atom extruded as a reactive silylene species has been trapped with diphenylacetylene in the Pd case to form, after chromatographic workup, a cis/trans mixture of the 4-oxa-3, 5-disilacyclopent-l-ene derivative. TheX-ray structure of the trans isomer shows the presence of two slightly pentacoordinated silicon atoms.