Bulletin of the Chemical Society of Japan p. 821 - 827 (1997)
Update date:2022-08-03
Topics:
Akitsu, Takashiro
Komorita, Seiko
Kushi, Yoshihiko
Li, Chunmin
Kanehisa, Nobuko
Kai, Yasushi
Copper(II) complexes [CuL2(i-PrNH2)2·H2O] (la), [CuL2(i-PrNH2)2] (Ib), [CuL2(EtNH2)2·H2O] (2a). [CuL2(EtNH2)2]-CHCl3 (2b), [CuL2(EtNH2)2·H2O)-2CHCl 3, (2c), and [CuL2(EtNH2)2·MeOH] (2d) (L = 5.5-diphenylhydantoinate) have been prepared. The crystal structures of la, 2c, and 2d were determined by X-ray analysis. Each CuKtO chromophore is a five-coordinated square-based pyramidal geometry. The axial Cu-O distances arc Cu(l)-O(1)(water) = 2.362(10) A, Cu(l)-O(l)(water) = 2.436(9) A and Cu(1)-O(1)(MeOH) = 2.33(1) A, for complexes la, 2c, and 2d, respectively. Intramolecular hydrogen bonds are formed between the carbonyl oxygens and amino hydrogens (C=O... H-N) as well as the axial ligand (C=O...H-O). The latter hydrogen bonds stabilize the axial ligand for coordination. Moreover, double intermolecular hydrogen bonds link the 5.5-diphenylhydantoinate ligands (C=O...H-N) belonging to be adjacent complex molecules in all three complexes. The electronic spectra of the complexes in the solid state and in chloroform solutions were determined at room temperature, and a considerable change in ligand field bands was observed. The five-coordinated complexes in the chloroform solutions release their axial water ligand and the CuN4O chromophore converts into a distorted tetrahedral CuN4 chromophore.
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