叔丁基亚磺酰基钨(CO)配合物与烯烃和炔烃的类过渡金属可逆环加成反应。
Transition-Metal-Like Reversible Cycloadditions of [tBuSP-W(CO) ] with Alkenes and Alkynes.
机构信息
College of Chemistry and Molecular Engineering, International Phosphorus Laboratory, International Joint Research Laboratory for, Functional Organophosphorus Materials of Henan Province, Zhengzhou University, Zhengzhou, 450001, P. R. China.
出版信息
Chemistry. 2019 Nov 27;25(66):15036-15039. doi: 10.1002/chem.201902948. Epub 2019 Oct 24.
tert-Butylthiophosphinidene complex [tBuSP-W(CO) ] was generated by dissociation of 1-(tert-butylthio)phosphirane-W(CO) complex under mild conditions. The formation of transient [tBuSP-W(CO) ] was indicated by trapping reactions with 2,3-dimethyl-1,3-butadiene, alkynes, phenanthrene-9,10-dione, and methanol. The LUMO of [MeSP-W(CO) ] is significantly lower in energy than those of [Me NP-W(CO) ], [MeOP-W(CO) ], and [Me PP-W(CO) ]. The HOMO of [MeSP-W(CO) ] contains a significant contribution from the in-plane lone pair of P and the LUMO shows a typical π* characteristic. Since stabilized by sulfur lone pair and coordinated by W(CO) , [tBuSP-W(CO) ] undergoes facile and reversible cycloadditions with alkenes and alkynes.
叔丁基膦杂环戊二烯基钨(CO)配合物[tBuSP-W(CO)]是在温和条件下由 1-(叔丁基硫)膦杂环戊二烯基钨(CO)配合物离解生成的。与 2,3-二甲基-1,3-丁二烯、炔烃、菲-9,10-二酮和甲醇的捕获反应表明瞬态[tBuSP-W(CO)]的形成。[MeSP-W(CO)]的 LUMO 能量明显低于[MeNP-W(CO)]、[MeOP-W(CO)]和[MePP-W(CO)]。[MeSP-W(CO)]的 HOMO 中 P 的平面孤对电子有很大的贡献，而 LUMO 显示出典型的π*特征。由于硫孤对电子的稳定作用和 W(CO)的配位作用，[tBuSP-W(CO)]与烯烃和炔烃容易发生可逆环加成反应。
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