The Highly Lewis Acidic Dicationic Phosphonium Salt: [(SIMes)PFPh
<sub>2</sub>
][B(C
<sub>6</sub>
F
<sub>5</sub>
)
<sub>4</sub>
]
<sub>2</sub>
作者:Michael H. Holthausen、Meera Mehta、Douglas W. Stephan
DOI:10.1002/anie.201403693
日期:2014.6.16
The dicationic imidazolium‐phosphoniumsalt [(SIMes)PFPh2][B(C6F5)4]2 has been prepared and shown to exhibit remarkable Lewis acidity in stoichiometric reactions and acting as an effective Lewisacid catalyst for the hydrodefluorination of fluoroalkanes and the hydrosilylation of olefins.
制备了咪唑鎓‐盐[(SIMes)PFPh 2 ] [B(C 6 F 5)4 ] 2,在化学计量反应中显示出显着的路易斯酸性,可作为有效的路易斯酸催化剂用于氟代烷烃的加氢脱氟和烯烃的氢化硅烷化。
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 derivedfrom 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( )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。