Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Analytical and Inorganic
Aggregation of Octahedral Thiolato Complexes by Forming Sulfur-Bridged Structures with Transition Metal Ions
Takumi Konno
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2004 Volume 77 Issue 4 Pages 627-649


The main developments in rational construction of chiral metallo-aggregates based on octahedral metal complexes with 2-aminoethanethiolate (aet) or L-cysteinate (L-cys), as well as their functionality as an S-donating chiral metalloligand, are reviewed in this paper. The reactions of the tris(thiolato)-type fac(S)-[M(aet or L-cys-N,S)3]0 or 3− (M = CoIII, RhIII, IrIII) with transition metal ions gave a variety of S-bridged metallo-aggregates, the structures and chiral properties of which are highly dependent on the nature of the reacting metal ions. The aggregation of the bis(thiolato)-type cis(S)-[Co(aet)2(en)]2+ was also performed through the replacement of a NiII ion in [Ni{Co(aet)2(en)}2]4+ by other transition metal ions. While aggregation of these tris(thiolato)- and bis(thiolato)-types of octahedral units commonly produced discrete S-bridged polynuclear structures, one-dimensional and two-dimensional extended polymeric structures, besides a discrete trinuclear structure, were constructed by the reactions of the mono(thiolato)-type [Co(aet or L-cys-N,S)(en)2]2+ or + with silver(I) ion, because of the adoption of μ3-thiolato bridging mode and/or the coordination ability of the free carboxylate group.

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© 2004 The Chemical Society of Japan
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