Optically Active S-Bridged CoIIIM (M = PtII, HgII, AuI) Polynuclear Complexes Derived from ΔΔ-[Ni{Co(aet)2(<i>R</i>-pn)}2]4+(aet = 2-Aminoethanethiolate, <i>R</i>-pn = (<i>R</i>)-1,2-Propanediamine)

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<jats:title>Abstract</jats:title> <jats:p>The substitution reaction of ΔΔ-[Ni{Co(aet)2(R-pn)}2]4+ (aet = 2-aminoethanethiolate, R-pn = (R)-1,2- propanediamine) with an equimolar K2[PtCl4] stereoselectively produced an optically active S-bridged trinuclear complex, ΔΔ-[Pt{Co(aet)2(R-pn)}2]4+ (1). A similar reaction with equimolar Hg(ClO4)2·6H2O also selectively gave the trinuclear complex, ΔΔ-[Hg{Co(aet)2(R-pn)}2]4+ (2). Contrary to 1 and 2, a tetranuclear complex, ΔΔ-[Au2{Co(aet)2(R-pn)}2]4+ (3), was obtained by a two-molar-equivalent addition of [AuCl{S(CH2CH2OH)2}]. The crystal structures of 1, 2, and 3 were determined by X-ray crystallography. Each of the Co atoms in 1, 2, and 3 is coordinated by one R-pn and two aet ligands to form an octahedron with a Δ configuration. The Pt atom in 1 is coordinated by four S atoms from two Δ-cis(S)-[Co(aet)2(R-pn)]+ units to take a square-planar geometry. Although the Hg atom in 2 is also surrounded by four S atoms from two Δ-cis(S)-[Co(aet)2(R-pn)]+ units, the geometry around the Hg center is of an appreciably distorted tetrahedron. On the other hand, each of the two Au atoms is bridged by an S atom from one cis(S)-[Co(aet)2(R-pn)]+ unit and an S atom from another unit to form a Co2Au2S4 eight-membered ring. These complexes are characterized based on the electronic absorption, CD, and 13C NMR spectra.</jats:p>

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