Features of Structure , Geometrical , and Spectral Characteristics of the ( HL ) 2

نویسنده

  • Olga V. Kovalchukova
چکیده

Coordinate compounds of copper(II) are widely spread both as biological objects (metalloproteins and metallo-enzymes), and in engineering. Among the functions of the copper proteins are: the electron transfer involving the Cu(I)/Cu(II) couple; monoterminaloxidases, which form either water or hydrogen peroxide from dioxygen; oxygenases, which incorporate an oxygen atom into a substrate; superoxide degradation to form dioxygen and peroxide; and the oxygen transport. From a structural point of view, there are three main types of biologically active copper centres found in the copper proteins (Cowan, 1993). These are “blue” copper centres, where copper atoms are normally coordinated to two nitrogens and two sulphurs, “non-blue” copper centres, where copper atoms are coordinated to two or three nitrogens as well as oxygens, and copper dimers. The nitrogens come from histidine groups, the sulfur from methionine and cysteine, the oxygens from the carboxyllic acid in the protein. So called “non-blue” and dimeric copper-containing proteins are of a a great similarity with complex halo (chloro-, bromo-) cuprates (Abolmaali et al., 1998). Thus, studies of structural and spectral characteristics of anionic complex halides of copper(II) can help to explain electronic structures as well as high reactional abilities and selectivities of active sites of copper-containing biopolymers in catalytic processes. It is also evident that anionic halocuprate(II) complexes are catalytically active species responsible for the increased reactivity in a lot of organic reactions (oxidation and polymerization of phenols, reactions of tertiary ammines, dimerization of primary alkyl groups et al.). Various investigations show that catalytic activities of complex copper(II) halides depend upon structures of their coordination polyhedra (Allen et al., 2009). And finally, cupric halo-complexes relate to classic magneto-active systems containing 3dmetals, magnetic properties of which significantly depend on features of the spatial structure of complex anions (Rakitin & Kalinnikov, 1994). d9-Electronic subshell of Cu(II) is responsible for distortions of symmetry of the coordination polyhedron (Gerloch & Constable, 1994). This deals with the Jahn-Teller effect (as a result of electron-vibrational interactions), and a large spin-orbital interaction constant. These two effects are of comparable values, and this fact complicates the prediction of structures of complexes of such types as well as physico-chemical properties and biological activity of Cu(II) complexes are in many respects determined by features of their structures.

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تاریخ انتشار 2012