Hydrosilylation of Olefins Catalyzed by Well-Defined Cationic Aluminum Complexes: Lewis Acid versus Insertion Mechanisms
作者:Kayla Jakobsson、Terry Chu、Georgii I. Nikonov
DOI:10.1021/acscatal.6b01694
日期:2016.11.4
The cationic aluminum complex [NacNacAlH]+ (2; NacNac = CHC(Me)N(2,6-Pri2C6H3)}2) can be easily generated from NacNacAlH2 by hydride abstraction and functions as a catalyst for the hydrosilylation of olefins and alkynes. Mechanistic studies suggest that, although olefin insertion into the Al–H bond is very facile, the catalysis does not proceed by an insertion/metathesis mechanism but likely by Lewis
阳离子铝络合物[NacNacAlH] +(2 ; NacNac = CH C(Me)N(2,6-Pr i 2 C 6 H 3)} 2)可以很容易地通过氢化物提取从NacNacAlH 2生成,并起着烯烃和炔烃氢化硅烷化的催化剂。机理研究表明,尽管烯烃插入Al-H键非常容易,但催化作用不是通过插入/复分解机制进行的,而是可能通过路易斯酸活化进行的。2的化学计量反应 炔烃提供了意想不到的跨NacNacAl部分加成C≡C的产物,生成了三脚架铝阳离子,这也是炔烃氢化硅烷化的有效催化剂。