Reactivity and stability of organocopper(I), silver(I), and gold(I) ate compounds and their trivalent derivatives.
Reactivity and stability of organocopper(I), silver(I), and gold(I) ate compounds and their trivalent derivatives.
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DOI：
10.1021/ja045659
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发表时间：
2005-01
影响因子：
15
通讯作者：
Waka Nakanishi;M. Yamanaka;E. Nakamura
中科院分区：
文献类型：
--
作者：
Waka Nakanishi;M. Yamanaka;E. Nakamura
有机铜酸盐(R（2)Cu(-)）试剂与碳亲电试剂反应形成新的C-C键，但它们的银和金对立物很少起这样的作用。借助混合密度泛函方法的量子力学计算，讨论了这种显著差异的起源。铜的反应通过两个步骤进行，即盐络合物R(2)Cu(I)（-）与亲电试剂E（+）的亲核反应和生成的R(2)(E)Cu（III）中间体的分解。对铜、银和金的这两个步骤进行了检验，以找出有机铜化合物优于银和金的原因。第一个反应是有利的，因为较高的d轨道直接参与亲核反应。由于高价铜的固有不稳定性，第二种反应与铜反应更快。
Organocuprate (R(2)Cu(-)) reagents react with a carbon electrophile to form a new C-C bond, yet their silver and gold counterparts seldom serve for such purposes. The origin of this striking difference is discussed with the aid of the quantum mechanical calculations using hybrid density functional method. The copper reaction takes place through two steps, the nucleophilic reaction of the ate complex R(2)Cu(I)(-) with an electrophile E(+) and the decomposition of the resulting R(2)(E)Cu(III) intermediate. These two steps were examined for Cu, Ag, and Au to find the reasons for the superiority of organocopper compounds to the silver and the gold counterparts. The first reaction is favored because of the higher-lying d-orbitals that directly participate in the nucleophilic reaction. The second reaction is faster with copper because of the intrinsic instability of the high valent copper species.