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• W2050000005 abstract "Abstract The contemporaneous reaction of copper(II) ‘salts’ with certain β-diones and N-substituted 1,2-diaminoethanes (enR) is reported. The influence of γ-position derivatives of 2,4-pentanedione, X-acacH (XH, CN, NO 2 ), is described and the contribution of anions to the stability, the stereochemistry and the electronic structure of the resulting mixed-ligand chelates is discussed. Spectroscopic observations disclose that the bidentate ligands form chelate rings with copper(II) as common vertex. Whenever the [Cu(β-dionato)enR] + entity pertains, the IR and the electronic excitation spectra, in conjunction with other physicochemical measurements, suggest that the CuN 2 O 2 chromophore attains a virtually square-planar structure. Copper(II) in the [Cu(β-dionato)enR] + entity lacks coordination saturation and, in addition to electrostatic interactions that prevail when bulky polyatomic anions counterbalance the positive charge, it is capable of forming covalent bonds with neutral molecules and charged species such as the halides and pseudohalides. The basal CuN 2 O 2 plane is distorted upon coordination of unidentate ligands residing on the apex of the resulting square-pyramidal structure. Further increase in the coordination number of copper(II) by bidentate anions or neutral molecules leads to tetragonally distorted octahedral structures. This change in the symmetry of the field induced on copper(II) is revealed by spectral shifts that also disclose covalent interactions in the encounters of the CuN 2 O 2 chromophore with polar or polarisable molecules. These interactions are enhanced with increasing ability of the attacking species to act as an electron pair donor. Linear dependence of the ligand field excitation maxima on the donicity of the attacking species is established. Rearrangement involving rapture of the CuO bond and formation of the CuN 4 chromophore accompanies the addition of N,N -dimethylethylenediamine, Me 2 en, to Cu(CN-acac) 2 . The charge in the resulting [Cu(Me 2 en) 2 ] 2+ entity is neutralised by the anion of the 3-cyano-2,4-pentanedione, CN-acac − , that binds to copper(II) through the nitrogen atom coordinating as nitrile. The coordination of a β-ketoenol as unidentate ligand through an atom other than oxygen or carbon has no precedence." @default.
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• W2050000005 date "1993-05-01" @default.
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• W2050000005 title "Counterion effects in the spectra and structure of solvatochromic copper(II) chelates containing 1,2-diamines and β-ketoenols" @default.
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• W2050000005 doi "https://doi.org/10.1016/s0020-1693(00)90708-4" @default.
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