Insertion of a Nontrigonal Phosphorus Ligand into a Transition Metal-Hydride: Direct Access to a Metallohydrophosphorane

被引：28
|
作者：
Tanushi, Akira [1 ]
Radosevich, Alexander T. [1 ]
机构：
[1] MIT, Dept Chem, 77 Massachusetts Ave, Cambridge, MA 02139 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 26期
关键词：
RAY CRYSTAL-STRUCTURE; H OXIDATIVE ADDITION; MOLECULAR-STRUCTURE; SUBSTITUTION-REACTIONS; RUTHENIUM COMPLEXES; CHEMISTRY; PLATINUM(II); REACTIVITY; EXCHANGE; REDOX;
D O I：
10.1021/jacs.8b05156
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The synthesis and reactivity of an NPN-chelating ligand containing a nontrigonal phosphorous triamide center (L1 = P(N(o-N(2-pyridyl)C6H4)(2)) is reported. Metalation of L1 with RuCl2 (PPh3)(3) gives RuCl2 (PPh3)-(L1) (2). By contrast, metalation of Ll with RuHCl-(CO)(PPh3)(3) yields RuCl(CO)(PPh 3)(L1(H)) (3), a chelated 10-P-5 ruthenahydridophosphorane, via net insertion into the Ru-H bond. Hydride abstraction from 3 with Ph3CPF6 gives [RuCl(CO)(PPh3)(L1)]PF6 (4); reaction of 4 with NaBH4 returns 3.
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页码：8114 / 8118
页数：5
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