Si-H addition followed by C-H bond activation induced by a terminal thorium imido metallocene: a combined experimental and computational study

被引：52

作者：

Ren, Wenshan ^{[1
,2
]}

Zhou, Enwei ^{[1
]}

Fang, Bo ^{[1
]}

Zi, Guofu ^{[1
]}

Fang, De-Cai ^{[1
]}

Walter, Marc D. ^{[3
]}

机构：

[1] Beijing Normal Univ, Dept Chem, Beijing 100875, Peoples R China

[2] Southwest Univ, Coll Chem & Chem Engn, Chongqing 400715, Peoples R China

[3] Tech Univ Carolo Wilhelmina Braunschweig, Inst Anorgan & Analyt Chem, D-38106 Braunschweig, Germany

来源：

CHEMICAL SCIENCE | 2014年 / 5卷 / 08期

基金：

中国国家自然科学基金;

关键词：

VALENT ORGANOURANIUM COMPLEXES; INTERMOLECULAR HYDROAMINATION; ELECTRONIC-STRUCTURE; MOLECULAR-STRUCTURE; HYDRIDE COMPLEX; URANIUM; REACTIVITY; ACTINIDE; CHEMISTRY; BIS(IMIDO);

D O I：

10.1039/c4sc00576g

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The Si-H bond addition to a terminal actinide imido complex was comprehensively studied. The base-free thorium imido [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th = N(p-tolyl) (1) activates Si-H bonds in PhSiH3 or Ph2SiH2 to give the thorium amido hydrido metallocenes [eta(5)-1,2,4(Me3C)(3)C5H2](2)Th(H)[N(p-tolyl) SiH2Ph] (2) and [eta(5)-1,2,4-(Me3C)(3)C5H2] Th-2(H)[N(p-tolyl)SiHPh2] (3), respectively. Complex 2 readily inserts unsaturated molecules into the Th-H bond, whereas complex 3 reversibly activates an intramolecular aromatic C-H bond to yield [eta(5)-1,2,4-(Me3C) 3C5H2](2)Th[eta(2)-N,C-{N(p-MeC6H3)(SiHPh2)}] (4) and H-2. The experimental results have been complemented by density functional theory (DFT) studies and provide a detailed understanding of the observed reactivity. In addition, a comparison between Th and early transition metals reveals that the Th4+ behaves more like an actinide than a transition metal.

引用

页码：3165 / 3172

页数：8

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