N-H Activation of Amines and Ammonia by Ru via Metal-Ligand Cooperation

被引：201

作者：

Khaskin, Eugene ^{[1
]}

Iron, Mark A. ^{[2
]}

Shimon, Linda J. W. ^{[2
]}

Zhang, Jing ^{[1
]}

Milstein, David ^{[1
]}

机构：

[1] Weizmann Inst Sci, Dept Organ Chem, IL-76100 Rehovot, Israel

[2] Weizmann Inst Sci, Dept Chem Res Support, IL-76100 Rehovot, Israel

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 25期

基金：

以色列科学基金会;

关键词：

OXIDATIVE ADDITION; SELECTIVE SYNTHESIS; C-H; WATER; ALCOHOLS; LIBERATION; IRIDIUM(I); REACTIVITY; COMPLEXES; AMINATION;

D O I：

10.1021/ja103130u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A nonoxidative addition pathway for the activation of NH bonds of ammonia Ru(II) complex is reported. The pincer complex 1 cleaves N-H bonds via metal-ligand cooperation involving aromatization of the pincer ligand without a change in the formal oxidation state of the metal. Electron-rich N-H bond substrates lead to reversible activation, while electron-poor substrates result in stable activation products. Isotopic labeling studies using ND3 as well as density functional theory calculations were used to shed light on the N-H activation mechanism.

引用

页码：8542 / +

页数：3

共 30 条

[1]

Beller M, 1999, CHEM-EUR J, V5, P1306, DOI 10.1002/(SICI)1521-3765(19990401)5:4<1306::AID-CHEM1306>3.0.CO

[2]

2-4

[3] Metal-ligand cooperation in C-H and H2 activation by an electron-rich PNPIr(I) system:: Facile ligand dearomatization-aromatization as key steps [J].