Orange and yellow crystals of copper(I) complexes bearing 8-(diphenylphosphino)quinoline: a pair of distortion isomers of an intrinsic tetrahedral complex.
Orange and yellow crystals of copper(I) complexes bearing 8-(diphenylphosphino)quinoline: a pair of distortion isomers of an intrinsic tetrahedral complex.
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DOI：
10.1021/ic1024636
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发表时间：
2011-05
影响因子：
4.6
通讯作者：
Takayoshi Suzuki;H. Yamaguchi;Akira Hashimoto;K. Nozaki;Mototsugu Doi;Naoya Inazumi;N. Ikeda;S. Kawata;M. Kojima;H. Takagi
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文献类型：
--
作者：
Takayoshi Suzuki;H. Yamaguchi;Akira Hashimoto;K. Nozaki;Mototsugu Doi;Naoya Inazumi;N. Ikeda;S. Kawata;M. Kojima;H. Takagi
双{8-（二苯基膦基）喹啉}铜（I）的四氟硼酸盐[Cu（Ph（2）Pqn）（2）]BF（4）得到橙子棱柱状（2 O）或黄色柱状（2 Y）晶体，这取决于所用溶剂和重结晶溶液的浓度。X射线衍射分析表明，2 O和2 Y晶体具有相同的组成，但具有不同的晶系：2 O为三斜晶系，空间群为P_1/1，Z = 2; 2 Y为单斜晶系，空间群为P_2（1）/c，Z = 4。在这些晶体中，四面体铜（I）配合物表现出强烈的“摇摆变形”的三角锥配位几何形状（通过滑动平移的不对称双齿螯合配体之一沿着四面体边缘）。此外，2 O和2 Y配合物都表现出“扁平畸变”，即两个螯合平面之间的二面角偏离垂直方向，并朝向相反的方向，这导致了一对畸变异构体：顺斜（sc：2 O）和反斜（ac：2 Y）。(31)P CP-MAS NMR谱表明2 O和2 Y可以区分。两种异构体均表现出不等价的P原子，但在2 Y中观察到较大的化学位移差异。TD-DFT计算再现了橙子和黄色络合物之间的光谱差异，这源于金属到配体的电荷转移跃迁。
The tetrafluoroborate salt of bis{8-(diphenylphosphino)quinoline}copper(I), [Cu(Ph(2)Pqn)(2)]BF(4), afforded orange prismatic (2O) or yellow columnar (2Y) crystals, dependent on the solvent and concentration of the recrystallization solution used. X-ray analysis revealed that crystals of 2O and 2Y had the same composition and exhibited different crystal systems: 2O was triclinic, with space group P ̅1 and Z = 2, and 2Y was monoclinic with space group P2(1)/c and Z = 4. In these crystals, the tetrahedral copper(I) complex exhibited a strong "rocking distortion" toward a trigonal pyramidal coordination geometry (by a slide translation of one of the unsymmetrical bidentate chelating ligands along the tetrahedral edge). In addition, both the 2O and 2Y complexes showed a "flattening distortion", meaning that the dihedral angle between the two chelate planes were off-perpendicular and oriented toward opposite directions, which resulted in a pair of distortion isomers: syn clinal (sc: 2O) and anti clinal (ac: 2Y). (31)P CP-MAS NMR spectroscopy indicated that 2O and 2Y could be distinguished. Both isomers exhibited inequivalent P atoms, but a larger difference in chemical shift was observed in 2Y. TD-DFT calculations reproduced the difference in spectra between the orange- and yellow-colored complexes, which originated from metal-to-ligand charge-transfer transitions.