Reversible Addition of the Si-H Bond of Phenylsilane to the Sc=N Bond of a Scandium Terminal Imido Complex

被引:43
|
作者
Chu, Jiaxiang [1 ]
Lu, Erli [1 ]
Chen, Yaofeng [1 ]
Leng, Xuebing [1 ]
机构
[1] Chinese Acad Sci, State Key Lab Organometall Chem, Shanghai Inst Organ Chem, Shanghai 200032, Peoples R China
基金
中国国家自然科学基金;
关键词
STRUCTURAL-CHARACTERIZATION; OLEFIN-METATHESIS; CATALYTIC HYDROAMINATION; ALKYLIDENE COMPLEXES; ACTIVATION; REACTIVITY; TITANIUM; CYCLOADDITION; ALKYNES; MECHANISMS;
D O I
10.1021/om3010349
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The facile and reversible addition of the Si-H bond of phenylsilane to the Sc=N bond of the scandium terminal imido complex [LSc=NDIPP(DMAP)] (1; L = [MeC(N(DIPP))CHC(Me)(NCH2CH2NMe)](-), DIPP = 2,6-(Pr2C6H3)-Pr-i) is reported. The reaction gives the scandium anilido hydride [LSc(H)(N(DIPP)(SiH2Ph))] (2), and a labeling experiment shows a rapid sigma-bond metathesis between Sc-H of the formed scandium anilido hydride and Si-H of phenylsilane during the reaction. 2 was trapped by an insertion reaction with diphenylcarbodiimide, giving the stable scandium anilido amidinate [LSc(N(DIPP)(SiH2Ph))(kappa(2)(N,N'-PhNCHNPh)] (3). Furthermore, the scandium terminal imido complex can efficiently catalyze the hydrosilylation of N-benzylidenepropan-1-amine. The reaction was completed within 2 h at 50 degrees C with 5 mol % of catalyst loading and highly selectively produced the monoaminosilane.
引用
收藏
页码:1137 / 1140
页数:4
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