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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• 作者：Takayoshi Suzuki ; Hiroshi Yamaguchi ; Akira Hashimoto ; Koichi Nozaki ; Mototsugu Doi ; Naoya Inazumi ; Noriaki Ikeda ; Satoshi Kawata ; Masaaki Kojima ; Hideo D. Takagi
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：May 2, 2011
• 年：2011
• 卷：50
• 期：9
• 页码：3981-3987
• 全文大小：947K
• 年卷期：v.50,no.9(May 2, 2011)
• ISSN：1520-510X

文摘

The tetrafluoroborate salt of bis{8-(diphenylphosphino)quinoline}copper(I), [Cu(Ph₂Pqn)₂]BF₄, 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 P1̅ and Z = 2, and 2Y was monoclinic with space group P2₁/c and Z = 4. In these crystals, the tetrahedral copper(I) complex exhibited a strong 鈥渞ocking distortion鈥?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 鈥渇lattening distortion鈥? 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). ³¹P 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.