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Open Chemistry
|
2008
|
vol. 6
|
issue 4
613-616
EN
A novel triply bridged dinuclear copper(I) complex: Cu2(μ-paa)(μ-dcpm)2(BF4)2·2CH2Cl2 [ paa = pyridine-2-carbaldehyde azine (C12H10N4) and dcpm = bis(dicyclohexylphosphino)methane(C25H46P2) ] has been synthesized and structurally characterized. Crystallographic studies of the complex showed that two copper(I) ions were bridged by one paa ligand and two dcpm ligands. The paa ligand adopted the Z configuration at the partially double N-N bond and the two copper ions have distorted tetrahedral coordination geometry. Because of the steric effect of dcpm, the pyridine rings of the paa ligand are obviously not on the same plane (the dihedral angle is 43.610). The interaction between neighboring ligands results in a N-N bond length (1.374(7) Å) contraction. The UV-vis spectra of the complex exhibited intense high-energy absorptions at λmax [...]
EN
A new ligand napaa (napaa = 7-acetamido-4-methyl-1,8-naphthyridin-2-carbaldehyde azine) and its two dinuclear copper(I) complexes, Cu2(napaa)(dppe)2(ClO4)2 (1) and Cu2(napaa)(PPh3)4(BF4)2 (2) (dppe = 1,2-bis(diphenylphosphino)ethane) and PPh3 = triphenylphosphine) were synthesized and characterized, and the structure of 1 was determined by X-ray crystal analysis. Each copper atom in 1 has a distorted tetrahedral geometry in which the metal center is associated to napaa and dppe ligands displaying chelating coordination modes and the naphthyridine rings of napaa are almost coplanar. The two complexes exhibit similar electronic absorption spectra with λmax at about 366 nm, which can be tentatively assigned to metal-to-ligand charge-transfer (MLCT) transition. The assignment was further supported by density functional theory (DFT) calculations. [...]
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