Syntheses, stereochemistry, reactivity, and some properties of sulfur-bridged cobalt(III)-cadmium(II) polynuclear complexes derived from mononuclear cobalt(III) complex with d-penicillaminate |
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Authors: | Yasunori Yamada Masayo TsumitaAki Hirano Yoshitaro MiyashitaKiyoshi Fujisawa Ken-ichi Okamoto |
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Institution: | Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan |
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Abstract: | A reaction of the octahedral bidentate metalloligand, trans(N)-Co(d-pen)2]− (d-pen=d-penicillaminate) with Cd(NO3)2 or Cd(ClO4)2 gave a novel S-bridged trinuclear complex, Cd(H2O){Co(d-pen)2}2] (1). In this complex molecule, the central Cd atom is surrounded by four S atoms from two Co(d-pen)2]− units and one O atom of a H2O molecule to form a distorted five-coordinated geometry. Each of two terminal Co(d-pen)2]− units takes an approximately octahedral geometry and has a similar trans(N) geometry to that of the starting material. On the other hand, the reaction of trans(N)-Co(d-pen)2]− with CdCl2 in the molar ratio of 1:1 gave an S-bridged dinuclear complex, CdCl{Co(d-pen)2}(H2O)m]·nH2O (m+n=4) (2). The reactivity of trans(N)-Co(d-pen)2]− toward CdCl2 is significantly influenced by the ratio of two components, and the formation of a similar trinuclear species to 1 is also suggested under the condition with excess amount of trans(N)-Co(d-pen)2]−. Some spectrochemical properties of these complexes are also discussed in relation to their structures. |
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Keywords: | Sulfur-bridged polynuclear complexes Cobalt(III) complexes Cadmium(II) complexes d-Penicillaminate complexes" target="_blank">d-Penicillaminate complexes Crystal structure Spectrochemistry |
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