A stable phosphanyl phosphaketene and its reactivity
A stable phosphanyl phosphaketene and its reactivity
复制标题
DOI：
10.1039/c4dt04012k
复制
发表时间：
2015-01-01
影响因子：
4
通讯作者：
Gruetzmacher, Hansjoerg
中科院分区：
文献类型：
--
作者：
Li, Zhongshu;Chen, Xiaodan;Gruetzmacher, Hansjoerg
磷乙醇钠，Na(OCP)，与体积庞大的对氯重氮磷反应生成磷酰磷乙酮，它在固态的惰性气氛中稳定数周。这种化合物最好的描述是一个紧密的离子对，具有非常长的P-P键距离(2.44埃)。在溶液中，这种磷甲酮在失去CO的情况下发生二聚反应，得到1，2，3-三磷杂环丁烷，经X-射线衍射法鉴定。作为中间体，五元杂环二膦与2，3-二甲基丁二烯发生Diels-Alder反应。用不同的密度泛函方法计算了该中间体在杂化配位中的形成以及二聚/CO损失，从而了解了反应机理。
Sodium phosphaethynolate, Na(OCP), reacts with the bulky P-chloro-diazaphosphole yielding a phosphanyl phosphaketene, which is stable for weeks under an inert atmosphere in the solid state. This compound is best described as a tight ion pair with a remarkably long P-P bond distance (2.44 angstrom). In solution, this phosphaketene dimerizes under loss of CO to give 1,2,3-triphosphabicyclobutane identified by an X-ray diffraction study. As an intermediate, a five-membered heterocyclic diphosphene was trapped in a Diels-Alder reaction with 2,3-dimethylbutadiene. The formation of this intermediate in a hetero-Coperearrangement as well as dimerization/CO loss were computed with various DFT methods which allowed us to understand the reaction mechanisms.