Preparation, Stereochemistry, and Reactivity of Linear-Type S-Bridged MCrIIIM (M = RhIII, IrIII) Trinuclear Complexes with 2-Aminoethanethiolate (aet). Crystal Structures of <i>ΔΛ</i>-[Cr{M(aet)3}2]3+

DOI PDF 13 Citations 26 References
  • Yoshitaro Miyashita
    Department of Chemistry, University of TsukubaTsukuba, Ibaraki 305
  • Narumi Sakagami
    Department of Chemistry, University of TsukubaTsukuba, Ibaraki 305
  • Yasunori Yamada
    Department of Chemistry, University of TsukubaTsukuba, Ibaraki 305
  • Takumi Konno
    Department of Chemistry, Faculty of Engineering, Gunma UniversityKiryu, Gunma 376
  • Jinsai Hidaka
    Department of Industrial Chemistry, Faculty of Engineering, Kinki University in KyushuIizuka, Fukuoka 820
  • Ken-ichi Okamoto
    Department of Chemistry, University of TsukubaTsukuba, Ibaraki 305

Description

<jats:title>Abstract</jats:title> <jats:p>S-Bridged trinuclear complexes, [CrIII{M(aet)3}2]3+, (M = RhIII (1), IrIII (2); aet = NH2CH2CH2S−) were newly prepared by the reaction of fac(S)-[M(aet)3] with chromium(III) nitrate. They were separated and optically resolved into the ΔΔ, ΛΛ, and ΔΛ isomers. Of these isomers for 1 and 2, the crystal structures of the ΔΛ isomers (1a and 2a) were determined by an X-ray diffraction method. Each of 1a and 2a consists of two fac(S)-[M(aet)3] subunits, a central Cr atom, three nitrates, and three water molecules, [Cr{M(aet)3}2](NO3)3·3H2O, in which three metals are aligned so as to be exactly linear. The central Cr atom is situated in an octahedral environment with the CrIIIS6 chromophore, which is formed by the coordination of two terminal fac(S)-[M(aet)3] units. The other isomers for 1 and 2 were characterized by the absorption and CD spectra, the molar conductivity, and the magnetic susceptibility. Each cyclic voltammogram of ΔΛ-[Cr{M(aet)3}2]3+ in water showed a reversible redox couple (M(IV)/M(III)) and an irreversible reduction wave (Cr(III)/Cr(II)). The stabilities of the S-bridged MCrIIIM complexes are also discussed in relation to the Cr–S bond strengths.</jats:p>

Journal

Citations (13)*help

See more

References(26)*help

See more

Keywords

Details 詳細情報について

Report a problem

Back to top