C-CN Bond Activation of Acetonitrile using Cobalt(I)

被引：34
作者：
Xu, Hongwei [1 ]
Williard, Paul G. [1 ]
Bernskoetter, Wesley H. [1 ]
机构：
[1] Brown Univ, Dept Chem, Providence, RI 02912 USA
来源：
ORGANOMETALLICS | 2012年 / 31卷 / 05期
基金：
美国国家科学基金会;
关键词：
CARBON-CARBON BONDS; THEORETICAL-EXAMINATION; ZEROVALENT NICKEL; CLEAVAGE; COMPLEXES; NITRILES; RHODIUM; CHEMISTRY; CYANO; ARYL;
D O I：
10.1021/om201270n
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
A cobalt(I) methyl species, (PMe3)(4)CoCH3, was found to promote C-CN bond oxidative addition of acetonitrile at ambient temperature. The isolated product of acetonitrile activation, cis,mer-(PMe3)(3)Co(CH3)(2)CN, was characterized by NMR, IR, and single-crystal X-ray diffraction studies and presents a higher valent metal in comparison to those previously observed for base-metal-mediated nitrile activations. A short-lived reaction intermediate was detected during nitrile cleavage and identified as fac-(PMe3)(3)Co(CH3)(2)CN, the kinetic product of C-CN oxidative addition. Conversion of the kinetic product to cis,mer(PMe3)(3)Co(CH3)(2)CN proceeds with a rate constant of [1.0(1)] X 10(-3) s(-1) at 27 degrees C.
引用
收藏
页码：1588 / 1590
页数：3
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