A Base-Free Terminal Actinide Phosphinidene Metallocene: Synthesis, Structure, Reactivity, and Computational Studies
A Base-Free Terminal Actinide Phosphinidene Metallocene: Synthesis, Structure, Reactivity, and Computational Studies
复制标题
无碱端锕系磷膦茂金属：合成、结构、反应性和计算研究
DOI：
10.1021/jacs.8b09746
复制
发表时间：
2018
影响因子：
15
通讯作者：
Walter Marc D.
中科院分区：
文献类型：
--
作者：
Zhang Congcong;Hou Guohua;Zi Guofu;Ding Wanjian;Walter Marc D.
对一种无碱的末端锕系膦茂金属的合成、结构和反应性能进行了全面的研究。在四氢呋喃（THF）中，钍的碘甲烷配合物Cp <$2Th（I）Me（2; Cp <$= η5- 1，2，4-（Me 3C）3C 5 H2）与Mes*PHK（Mes* = 2，4，6-（Me 3C）3C 6 H2）发生盐复分解反应，得到了第一个稳定的无碱端膦锕系茂金属Cp <$2Th <$PMes*（3）.密度泛函理论（DFT）表明，Cp_2 Th ~（2+）与[PMes*]~（2-）之间的键比相关的钍亚胺配合物中的键更共价.虽然膦叉络合物3对炔没有反应性，但它与各种杂环饱和分子如CS2、异硫氰酸酯、腈、异腈和有机叠氮化物反应，形成硫代磷酸酯、亚氨基络合物、金属氮杂环丙烷和叠氮化合物。这些实验观测得到了DFT计算的补充。
The synthesis, structure, and reactivity of a base-free terminal actinide phosphinidene metallocene have been comprehensively studied. The salt metathesis reaction of the thorium methyl iodide complex Cp‴2Th(I)Me (2; Cp‴ = η5-1,2,4-(Me3C)3C5H2) with Mes*PHK (Mes* = 2,4,6-(Me3C)3C6H2) in THF furnishes the first stable base-free terminal phosphinidene actinide metallocene, Cp‴2Th═PMes* (3). Density functional theory (DFT) shows that the bonds between the Cp‴2Th2+and [PMes*]2–fragments are more covalent than those in the related thorium imido complex. While the phosphinidene complex3shows no reactivity toward alkynes, it reacts with a variety of heterounsaturated molecules such as CS2, isothiocyanate, nitriles, isonitriles, and organic azides, forming carbodithioates, imido complexes, metallaaziridines, and azido compounds. These experimental observations are complemented by DFT computations.