Ferrocene‐Based Phosphenium Ion with Intramolecular Phosphine Coordination
Ferrocene‐Based Phosphenium Ion with Intramolecular Phosphine Coordination
复制标题
具有分子内膦配位的二茂铁基磷离子
DOI：
10.1002/ejic.202100615
复制
发表时间：
2021
影响因子：
2.3
通讯作者：
Sasamori Takahiro
中科院分区：
文献类型：
--
作者：
Zhang Tianqing;Lee Vladimir Ya.;Morisako Shogo;Aoyagi Shinobu;Sasamori Takahiro
合成了一种具有分子内膦配位的双（二茂铁基）膦离子，并将其引入[2]二茂铁并菲骨架中，作为一种空气稳定的化合物。虽然它可以被认为是膦基-磷鎓衍生物，但考虑到二茂铁部分的α基团的潜在旋转，分离的化合物应该是具有分子内膦配位的掩蔽的磷鎓离子。通过CV测量和理论计算揭示了孤立的膦配位的膦离子的氧化还原行为，表明其在二茂铁基部分的氧化和在磷中心的还原连续地产生相应的氧膦基自由基和磷化物离子。
A bis(ferrocenyl)phosphenium ion with intramolecular phosphine‐coordination, incorporated within [2]ferrocenophane framework, was synthesized as an air‐stable compound. Although it can be thought as a phosphino‐phosphonium derivative, considering the potential rotation of the cyclopentadienyl group of the ferrocene moiety, the isolated compound should be a masked phosphenium ion with intramolecular phosphine coordination. The redox behavior of the isolated phosphine‐coordinated phosphenium ion has been revealed by CV measurements and the theoretical calculations, suggesting its oxidation at the ferrocenyl moieties and reduction at the phosphorus center consecutively giving the corresponding phosphinyl radical and phosphide ion.