Abstract
A comparative study of the three-dimensional and electronic structures of the chelate salts (ML n ) of enol forms of α-cyano-substituted α-phosphoryl- and α-(thiophosphoryl)acetones (RO)2P(X)C(CN)C=CMe(OH) (X = O or S; R = Pr or Et) with the CuI, CuII, and CoII cations was carried out. In all complexes under consideration, the geometry of the central moiety of the O—C(Me)—C(CN)—P chelate-bridging ligand remains unchanged. The substantial electron delocalization involving the cyano group is observed in the O—C—C(CN)—P(X) ligand framework. The structure of the bis-chelate Cu[(PrO)2P(O)C(CN)C(O)Me]2 complex was established by X-ray diffraction analysis at 180 K and vibrational (IR and Raman) spectroscopy. The study in the temperature range from 290 to 140 K revealed the phase transition at 200 K accompanied by a change in the coordination polyhedron about the copper cation from a symmetrical octahedron (4+2 coordination) to a strongly unsymmetrically distorted octahedron (4+1+1 coordination). In both crystal modifications, four oxygen atoms form the base of the octahedron, and the axial positions are occupied by the nitrogen atoms.
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