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首页> 外文期刊>Acta Crystallographica, Section B. Structural Science >Nucleophilic addition reaction in coordinated non-linear pseudohalides: experimental charge density analysis in trans-bis(cyanamidonitrato-N : O)bis(imidazole-N-3)copper(II) complex
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Nucleophilic addition reaction in coordinated non-linear pseudohalides: experimental charge density analysis in trans-bis(cyanamidonitrato-N : O)bis(imidazole-N-3)copper(II) complex

机译：配位的非线性拟卤化物中的亲核加成反应：反式双（氰胺基-N：O）双（咪唑-N-3）铜（II）配合物中的实验电荷密度分析

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摘要

The experimental crystal charge density of the complex [Cu(iz)(2) (can)(2)] (I) (where iz = imidazole, can = cyanamidonitrate anion), [Cu(C3H4N2)(2) (CN3O2)(2)], crystallizing in centrosymmetric space group P2(1)/c, has been determined at 120.0 (2) K, using Hansen and Coppens' aspherical atom multipole model. The central Cu atom is pseudo-octahedrally coordinated by four N atoms in an equatorial plane [two from iz molecules, 1.9660 (4) Angstrom, two from can anions, 2.0273 (5) Angstrom] and by two O atoms (from two adjacent molecules) in axial positions [2.5566 (5) Angstrom]. The d-orbital population analysis shows that the oxidation state for the copper is +2 with the d(9) configuration and that there is a hole in the d(x)2(-y)2 orbital, located in the plane of the four nitrogen-ligating atoms. Electron lone pairs of these four N atoms are pointing into these regions of depleted electron density. In accordance with the medium-length Cu-O axial bonds, the d(z)z orbital is almost fully occupied [1.79 (3) electrons]. The non-bonding d(xy) orbital is fully occupied [2.05 (3) electrons]. Analysis of the atomic charges does indicate a deficit of +0.35 (4) e(-) on the nitrile carbon, which provides evidence of beta-carbon activation for a possible nucleophilic addition reaction. This reaction has been indirectly confirmed experimentally. [References: 29]
机译：配合物[Cu（iz）（2）（can）（2）]（I）的实验晶体电荷密度（其中iz =咪唑，can =氰胺酸根阴离子），[Cu（C3H4N2）（2）（CN3O2）（ [2）]使用Hansen和Coppens的非球面原子多极模型确定了在中心对称空间群P2（1）/ c中的结晶度为120.0（2）K。中心的Cu原子由赤道平面中的四个N原子伪八面体配位[两个来自iz分子，是1.9660（4）埃，两个是来自can阴离子，是2.0273（5）埃]，并且是两个O原子（来自两个相邻的分子） ）在轴向位置[2.5566（5）埃]。 d轨道总体分析表明，在d（9）构型下，铜的氧化态为+2，并且在d（x）2（-y）2轨道上有一个孔，位于四个氮连接原子。这四个N原子的电子孤对指向这些电子密度耗尽的区域。根据中等长度的Cu-O轴向键，d（z）z轨道几乎完全占据[1.79（3）个电子]。非结合d（xy）轨道被完全占据[2.05（3）个电子]。原子电荷的分析确实表明腈碳缺乏+0.35（4）e（-），这为可能的亲核加成反应提供了β-碳活化的证据。该反应已通过实验间接证实。 [参考：29]

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