Singlet (Phosphino)phosphinidenes are Electrophilic
Singlet (Phosphino)phosphinidenes are Electrophilic
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DOI：
10.1021/jacs.6b04232
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发表时间：
2016-07-13
影响因子：
15
通讯作者：
Bertrand, Guy
中科院分区：
文献类型：
--
作者：
Hansmann, Max M.;Jazzar, Rodolphe;Bertrand, Guy
室温稳定的（膦基）亚膦烯与一氧化碳、稳定的单重态卡宾（包括差的π-接受咪唑-2-亚基）和膦反应，分别产生相应的磷烯酮、亚膦-卡宾和亚膦-膦加合物。而电子基态计算表明PP多重键字符，其中的终端磷是带负电荷的，所观察到的反应性清楚地表明，（膦基）膦酰亚胺是亲电子的，如预期的缺电子物种。竞争实验和福井函数的计算结果进一步证明了这一点。
A room-temperature stable (phosphino)phosphinidene reacts with carbon monoxide, stable singlet carbenes, including the poor pi-accepting imidazol-2-ylidene, and phosphines giving rise to the corresponding phosphaketene, phosphinidene-carbene and phosphinidene-phosphine adducts, respectively. Whereas the electronic ground-state calculations indicate a PP multiple bond character in which the terminal phosphorus is negatively charged, the observed reactivity clearly indicates that (phosphino)phosphinidenes are electrophilic as expected for an electron-deficient species. This is further demonstrated by competition experiments as well as by the results of Fukui function calculations.