Novel S-Bridged CoIIIPdII Polynuclear Complexes Derived from [NiII{CoIII(aet)2(en)}2]Cl4 (aet = 2-Aminoethanethiolate). Crystal Structures of [Pd{Co(aet)2(en)}2]Cl4 and [PdCl2{Co(aet)2(en)}]Cl

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  • Takumi Konno
    Department of Chemistry, Faculty of Engineering, Gunma UniversityKiryu, Gunma 376
  • Takayuki Machida
    Department of Chemistry, University of TsukubaTsukuba, Ibaraki 305
  • Ken-ichi Okamoto
    Department of Chemistry, University of TsukubaTsukuba, Ibaraki 305

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<jats:title>Abstract</jats:title> <jats:p>The reaction of an S-bridged CoIIINiIICoIII trinuclear complex, [Ni{Co(aet)2(en)}2]Cl4 (1), with Na2[PdCl4] in a ratio of 1 : 1 gave an S-bridged CoIIIPdIICoIII trinuclear complex, [Pd{Co(aet)2(en)}2]Cl4 (2), while the corresponding 1 : 2 reaction produced an S-bridged CoIIIPdII dinuclear complex, [PdCl2{Co(aet)2(en)}]Cl (3). The crystal structures of 2 and 3 were determined by X-ray crystallography: 2·6H2O crystallizes in the monoclinic space group C2/c with a = 14.951(2), b = 19.753(2), c = 12.926(2) Å, β = 113.33(1) °, V = 3505.4(9) Å3, Z = 4, and R = 0.034. 3·2H2O crystallizes in the monoclinic space group P21/n with a = 14.282(5), b = 8.497(2), c = 16.139(6) Å, β = 115.13(1) °, V = 1773(1) Å3, Z = 4, and R = 0.026. In 2 the PdII atom is coordinated by four S atoms from two C2-cis(S)-[Co(aet)2(en)]+ units, while the PdII atom in 3 is coordinated by two Cl atoms besides two S atoms from one octahedral C2-cis(S)-[Co(aet)2(en)]+ unit. 2 was readily converted to 3 by the reaction with Na2[PdCl4], while the conversion of 3 to 2 was achieved by reacting 3 with 1. 2 and 3 were optically resolved and their electronic absorption and CD spectral behavior is also reported.</jats:p>

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