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DOI: 10.1039/A809753D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 2151-2158

Synthesis, characterisation and polynuclearisation reaction of trans(S)-[Co(aminothiolate-N,S[hair space])2(en)]-type cobalt(III) complexes with 2-aminoethanethiolate, L-cysteinate and D-penicillaminate

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Toshiaki Yonemura, Zhi-Ping Bai, Ken-ichi Okamoto, Tomoharu Ama, Hiroshi Kawaguchi, Takaji Yasui and Jinsai Hidaka

Abstract

The trans(S)-[Co(N)4(S)2]-type mononuclear complexes [Co(L)2(en)]+ or – (L = 2-aminoethanethiolate (aet) 1, L-cysteinate (L-cys) 3 or D-penicillaminate (3-sulfanyl-D-valinate) (D-pen) 5) were newly prepared by the reaction of trans-[CoCl2(en)2]+ with L at pH 8.5 and 25 °C. The crystal structure of 1 was determined by X-ray diffraction analysis. The geometry around the cobalt atom is approximately octahedral and two thiolate donor atoms in the aet ligands occupy trans positions to each other. Two Co–S bonds are lengthened by the double sulfur trans influence across the cobalt centre attributable to two thiolato sulfur donor atoms. The diastereomers of 3 and 5 were separated by the column chromatographic technique and characterised on the basis of their UV/Vis, CD and 13C NMR spectra. The ΛDD isomer of 5 (5ΛDD) is preferably formed by attractive (COO[hair space][hair space]· · ·[hair space][hair space]H–N–H) interactions. Though cis(S)-[Co(L)2(en)]+ or – (L = aet 2, L-cys 4 or D-pen 6) were also produced by the same preparative reaction, they could not be separated into the geometrical isomers because of very rapid isomerisation and/or polynuclearisation reaction during elution from the column. It is clear that all trans(S) complexes also show drastic and characteristic UV/Vis spectral changes with time in aqueous solutions and tend to isomerise to the cis(S) isomer, followed by the formation of S-bridged polynuclear complexes owing to both the double sulfur trans influence and high nucleophilicity of the thiolate donor atoms. The polynuclearisation reactions of the three trans(S) isomers proceed according to different processes depending on their ligands. In the polynuclearisation reaction of 3, especially, the novel dinuclear complex ΛLLL-[Co{Co(L-cys-N,S[hair space])3}(L-cys-N,O,S[hair space])]2–7, which has not so far been identified in usual dinuclearisation reactions, was newly obtained.

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