Synthesis, characterization, and stereochemistry of S-bridged Co IIIMCoIII (M = PdII, PtII) trinuclear complexes containing two non-bridging thiolato groups: Building blocks for the construction of chiral heterometallic aggregatest

Yu Chikamoto, Masakazu Hirotsu, Tadashi Yamaguchi, Takashi Yoshimura, Takumi Konno

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    15 Citations (Scopus)

    Abstract

    The reaction of fac(S)-[Co(aet)3] (aet = aminoethanethiolate) with [PdCl4]2- in a 2:1 ratio in water gave an S-bridged CoIIIPdIICoIII trinuclear complex composed of two mer(S)-[Co(aet)3] units, [Pd{Co(aet)3} 2]2+ ([I]2+). In [1]2+, each of the two mer(S)-[Co(aet)3] units is bound to a square-planar Pd II ion through two of three thiolato groups, leaving two non-bridging thiolato groups at the terminal. Of two geometrical forms, syn and anti, possible for [Pd{Co(aet)3}2]2-, which arise from the difference in arrangement of two terminal non-bridging thiolato groups, [1]2+ afforded only the syn form. A similar reaction of fac(S)-[Co(aet)3] with [PtCl4]2- or trans-[PtCl2(NH3)2] produced an analogous CoIIIPtIICoIII trinuclear complex, [Pt{Co(aet)3}2]2+ ([2]2+), but both the syn and anti forms were formed for [2]2+. Complexes [1] 2+ and syn- and anti-[2]2+, which exclusively exist as a racemic (ΔΔ/ΛΛ) form, were successfully optically resolved with use of [Sb2(R,R-tartrato)2]2- as the resolving agent. The reaction of syn-[2]2+ with [AuCl{S(CH 2CH2OH)2}] led to the formation of an S-bridged Co4 IIIPt2 IIAu2 1 octanuclear metallacycle, [Au2{Pt[Co(aet) 3]2}2]6+ ([3]6+), while the corresponding reaction of anti-[2]2+ afforded a different product ({[4]3+}n) that is assumed to have a polymeric structure in {[Au{Pt[Co(aet)3]2}]3+}n.

    Original languageEnglish
    Pages (from-to)3654-3661
    Number of pages8
    JournalDalton Transactions
    Issue number21
    DOIs
    Publication statusPublished - 2004 Nov 7

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    Stereochemistry
    Ions
    Water
    platinum tetrachloride

    ASJC Scopus subject areas

    • Chemistry(all)

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    @article{f0ad38b102784399b3340cf7c862b3f1,
    title = "Synthesis, characterization, and stereochemistry of S-bridged Co IIIMCoIII (M = PdII, PtII) trinuclear complexes containing two non-bridging thiolato groups: Building blocks for the construction of chiral heterometallic aggregatest",
    abstract = "The reaction of fac(S)-[Co(aet)3] (aet = aminoethanethiolate) with [PdCl4]2- in a 2:1 ratio in water gave an S-bridged CoIIIPdIICoIII trinuclear complex composed of two mer(S)-[Co(aet)3] units, [Pd{Co(aet)3} 2]2+ ([I]2+). In [1]2+, each of the two mer(S)-[Co(aet)3] units is bound to a square-planar Pd II ion through two of three thiolato groups, leaving two non-bridging thiolato groups at the terminal. Of two geometrical forms, syn and anti, possible for [Pd{Co(aet)3}2]2-, which arise from the difference in arrangement of two terminal non-bridging thiolato groups, [1]2+ afforded only the syn form. A similar reaction of fac(S)-[Co(aet)3] with [PtCl4]2- or trans-[PtCl2(NH3)2] produced an analogous CoIIIPtIICoIII trinuclear complex, [Pt{Co(aet)3}2]2+ ([2]2+), but both the syn and anti forms were formed for [2]2+. Complexes [1] 2+ and syn- and anti-[2]2+, which exclusively exist as a racemic (ΔΔ/ΛΛ) form, were successfully optically resolved with use of [Sb2(R,R-tartrato)2]2- as the resolving agent. The reaction of syn-[2]2+ with [AuCl{S(CH 2CH2OH)2}] led to the formation of an S-bridged Co4 IIIPt2 IIAu2 1 octanuclear metallacycle, [Au2{Pt[Co(aet) 3]2}2]6+ ([3]6+), while the corresponding reaction of anti-[2]2+ afforded a different product ({[4]3+}n) that is assumed to have a polymeric structure in {[Au{Pt[Co(aet)3]2}]3+}n.",
    author = "Yu Chikamoto and Masakazu Hirotsu and Tadashi Yamaguchi and Takashi Yoshimura and Takumi Konno",
    year = "2004",
    month = "11",
    day = "7",
    doi = "10.1039/b409614b",
    language = "English",
    pages = "3654--3661",
    journal = "Dalton Transactions",
    issn = "1477-9226",
    publisher = "Royal Society of Chemistry",
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    TY - JOUR

    T1 - Synthesis, characterization, and stereochemistry of S-bridged Co IIIMCoIII (M = PdII, PtII) trinuclear complexes containing two non-bridging thiolato groups

    T2 - Building blocks for the construction of chiral heterometallic aggregatest

    AU - Chikamoto, Yu

    AU - Hirotsu, Masakazu

    AU - Yamaguchi, Tadashi

    AU - Yoshimura, Takashi

    AU - Konno, Takumi

    PY - 2004/11/7

    Y1 - 2004/11/7

    N2 - The reaction of fac(S)-[Co(aet)3] (aet = aminoethanethiolate) with [PdCl4]2- in a 2:1 ratio in water gave an S-bridged CoIIIPdIICoIII trinuclear complex composed of two mer(S)-[Co(aet)3] units, [Pd{Co(aet)3} 2]2+ ([I]2+). In [1]2+, each of the two mer(S)-[Co(aet)3] units is bound to a square-planar Pd II ion through two of three thiolato groups, leaving two non-bridging thiolato groups at the terminal. Of two geometrical forms, syn and anti, possible for [Pd{Co(aet)3}2]2-, which arise from the difference in arrangement of two terminal non-bridging thiolato groups, [1]2+ afforded only the syn form. A similar reaction of fac(S)-[Co(aet)3] with [PtCl4]2- or trans-[PtCl2(NH3)2] produced an analogous CoIIIPtIICoIII trinuclear complex, [Pt{Co(aet)3}2]2+ ([2]2+), but both the syn and anti forms were formed for [2]2+. Complexes [1] 2+ and syn- and anti-[2]2+, which exclusively exist as a racemic (ΔΔ/ΛΛ) form, were successfully optically resolved with use of [Sb2(R,R-tartrato)2]2- as the resolving agent. The reaction of syn-[2]2+ with [AuCl{S(CH 2CH2OH)2}] led to the formation of an S-bridged Co4 IIIPt2 IIAu2 1 octanuclear metallacycle, [Au2{Pt[Co(aet) 3]2}2]6+ ([3]6+), while the corresponding reaction of anti-[2]2+ afforded a different product ({[4]3+}n) that is assumed to have a polymeric structure in {[Au{Pt[Co(aet)3]2}]3+}n.

    AB - The reaction of fac(S)-[Co(aet)3] (aet = aminoethanethiolate) with [PdCl4]2- in a 2:1 ratio in water gave an S-bridged CoIIIPdIICoIII trinuclear complex composed of two mer(S)-[Co(aet)3] units, [Pd{Co(aet)3} 2]2+ ([I]2+). In [1]2+, each of the two mer(S)-[Co(aet)3] units is bound to a square-planar Pd II ion through two of three thiolato groups, leaving two non-bridging thiolato groups at the terminal. Of two geometrical forms, syn and anti, possible for [Pd{Co(aet)3}2]2-, which arise from the difference in arrangement of two terminal non-bridging thiolato groups, [1]2+ afforded only the syn form. A similar reaction of fac(S)-[Co(aet)3] with [PtCl4]2- or trans-[PtCl2(NH3)2] produced an analogous CoIIIPtIICoIII trinuclear complex, [Pt{Co(aet)3}2]2+ ([2]2+), but both the syn and anti forms were formed for [2]2+. Complexes [1] 2+ and syn- and anti-[2]2+, which exclusively exist as a racemic (ΔΔ/ΛΛ) form, were successfully optically resolved with use of [Sb2(R,R-tartrato)2]2- as the resolving agent. The reaction of syn-[2]2+ with [AuCl{S(CH 2CH2OH)2}] led to the formation of an S-bridged Co4 IIIPt2 IIAu2 1 octanuclear metallacycle, [Au2{Pt[Co(aet) 3]2}2]6+ ([3]6+), while the corresponding reaction of anti-[2]2+ afforded a different product ({[4]3+}n) that is assumed to have a polymeric structure in {[Au{Pt[Co(aet)3]2}]3+}n.

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