Olefin Isomerization and Hydrosilylation Catalysis by Lewis Acidic Organofluorophosphonium Salts
作者:Manuel Pérez、Lindsay J. Hounjet、Christopher B. Caputo、Roman Dobrovetsky、Douglas W. Stephan
DOI:10.1021/ja410379x
日期:2013.12.11
= 0, 1) exhibit Lewis acidity derived from a low-lying σ* orbital at P opposite F. This acidity is evidenced by the reactions of these salts with olefins, which catalyze the rapid isomerization of 1-hexene to 2-hexene, the cationic polymerization of isobutylene, and the Friedel-Crafts-type dimerization of 1,1-diphenylethylene. In the presence of hydrosilanes, olefins and alkynes undergo efficient hydrosilylation
式 [(C6F5)(3-x)Ph(x)PF][B(C6F5)4] (x = 0, 1) 的有机氟鏻盐表现出路易斯酸性,源自低位 σ* 轨道在 P 与 F 相对这种酸性通过这些盐与烯烃的反应得到证明,烯烃催化 1-己烯快速异构化为 2-己烯、异丁烯的阳离子聚合以及 1,1-二苯基乙烯的 Friedel-Crafts 型二聚反应。在氢硅烷的存在下,烯烃和炔烃发生有效的氢化硅烷化催化作用,生成烷基硅烷。该机制的实验和计算考虑与氢硅烷在不饱和 CC 键上的顺序活化和 1,2-加成一致。