Orange and Yellow Crystals of Copper(I) Complexes Bearing 8-(Diphenylphosphino)quinoline: A Pair of Distortion Isomers of an Intrinsic Tetrahedral Complex

Takayoshi Suzuki, Hiroshi Yamaguchi, Akira Hashimoto, Koichi Nozaki, Mototsugu Doi, Naoya Inazumi, Noriaki Ikeda, Satoshi Kawata, Masaaki Kojima, Hideo D. Takagi

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Abstract

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 P1̄ 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 "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). 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.

Original languageEnglish
Pages (from-to)3981-3987
Number of pages7
JournalInorganic Chemistry
Volume50
Issue number9
DOIs
Publication statusPublished - May 2 2011

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Suzuki, T., Yamaguchi, H., Hashimoto, A., Nozaki, K., Doi, M., Inazumi, N., Ikeda, N., Kawata, S., Kojima, M., & Takagi, H. D. (2011). Orange and Yellow Crystals of Copper(I) Complexes Bearing 8-(Diphenylphosphino)quinoline: A Pair of Distortion Isomers of an Intrinsic Tetrahedral Complex. Inorganic Chemistry, 50(9), 3981-3987. https://doi.org/10.1021/ic1024636