Phosphide delivery to a cyclotrisilene.
Phosphide delivery to a cyclotrisilene.
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DOI：
10.1002/anie.201409908
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发表时间：
2015-01-07
期刊：
影响因子：
--
通讯作者：
Goicoechea JM
中科院分区：
文献类型：
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作者：
Robinson TP;Cowley MJ;Scheschkewitz D;Goicoechea JM
报道了2-磷炔阴离子（PCO−）对环状三硅烯（cSi 3（Tip）4）的反应性。结果是前体的P=C和Si=Si多重键的净活化，得到杂原子双环[1.1.1]戊-2-酮类似物（[P（CO）Si 3（Tip）4]-; 1）。该反应可以解释为磷化物和羰基在Si=Si双键上的形式加成。光解脱羰1的结果在纳入的磷化顶点到cyclotrisilene支架，产生的同源物的环丁烯阴离子具有相当大的烯丙基字符。
The reactivity of the 2-phosphaethynolate anion (PCO−) towards a cyclic trisilene (cSi3(Tip)4) is reported. The result is the net activation of the P=C and Si=Si multiple bonds of the precursors affording a heteroatomic bicyclo[1.1.1]pentan-2-one analogue ([P(CO)Si3(Tip)4]−; 1). This reaction can be interpreted as the formal addition of a phosphide and a carbonyl across the Si=Si double bond. Photolytic decarbonylation of 1 results in the incorporation of the phosphide vertex into the cyclotrisilene scaffold, yielding a congener of the cyclobutene anion with considerable allylic character.