Dinuclear copper complexes of pyridylphenylphosphine ligands: Characterization of a mixed-valence CuII/CuI dimer

Homo bi-copper complexes [Cu2{PhP(2-py)2}2(NO3)3] (1) and [Cu2{P(2-py)3}2Cl2] (2), were synthesized from the reaction of Cu(NO3)2·3H2O and CuCl2·2H2O with their corresponding 2-pyridylphosphine ligands. Compound 1 has a mixed valence Cu(I)–Cu(II) core with electron acceptor phosphine atoms and two NO3− anions coordinated in a monodentate fashion to Cu(I), giving it a distorted tetrahedral geometry. The environment of Cu(II) in 1 is composed of four nitrogen atoms from pyridyl and another NO3− anion in a square pyramidal geometry. This complex shows luminescence and a low energy absorption band at 969 nm corresponding to intermetallic electron transfer between the copper centers. Complex 2 was prepared from the treatment of copper(II) chloride with tris(2-pyridyl)phosphine, producing a binuclear copper complex which possesses a crystallographic inversion center. The copper geometry in this complex is distorted tetrahedral with coordination of one Cl−, two nitrogens from one bridging tris(2-pyridyl)phosphine ligand and one P atom from the other bridging tris(2-pyridyl)phosphine ligand, in a similar way observed in related complexes. The products have been characterized by spectroscopic methods and also by the single-crystal X-ray diffraction method.

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► Dinuclear copper complexes of pyridylphenylphosphine were synthesized.
► Luminescence and a low energy absorption band correspond to intermetallic electron transfer.
► Computational studies along with X-ray and spectroscopy show formation of mixed valence complexes of Cu(I) and Cu(II).