The University of Osaka · Materials Science
Professor Takumi Konno's research lab specializes in the rational design and synthesis of chiral multinuclear and metallosupramolecular architectures based on transition metal complexes, particularly those incorporating sulfur-donor ligands such as 2-aminoethanethiolate (aet) and l-cysteinate. The lab focuses on creating S-bridged metallo-aggregates and heterobimetallic complexes with well-defined stereochemistry, exploring their optical activity, structural diversity, and functionality as multidentate chiral metalloligands. A key direction involves the development of novel heterometallic coordination polymers and cluster compounds with potential applications in asymmetric catalysis and electrocatalysis.
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Abstract 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 whic
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and properties of T-cage-type S-bridged rhodium(III)zinc(II) octanuclear complexes with 2-aminoethanethiolate of L-cysteinateTakumi Konno, Kenichi Okamoto, and Jinsai HidakaCite this: Inorg. Chem. 1994, 33, 3, 538–544Publication Date (Print):February 1, 1994Publication History Published online1 May 2002Published inissue 1 February 1994https://pubs.acs.org/doi/10.1021/ic00081a023https://doi.org/10.1021/ic00081a023research-articleACS Publicatio
Developments in the rational creation of chiral multinuclear and metallosupramolecular compounds based on linear-type metal complexes with penicillaminate (pen), as well as their functionality as a multidentate chiral metalloligand, is the main subject of this paper. The reactions of a mononuclear Au(I) complex, [Au(d-pen)(2)](3-), in which two d-pen ligands bind to an Au(I) center through thiolato S atoms, with transition metal ions afford a variety of S-bridged heterobimetallic multinuclear co
Heterometallic coordination polymers have been rapidly developed as heterogeneous electrocatalysts. This review highlights the synthesis strategies of these polymers and the relationships between structures and electrocatalytic performances.
Abstract The reactions of fac-[Rh(aet)3] (aet=2-aminoethanethiolate) or ΔLLL-fac-[Rh(l-cys-N,S)3]3− (l-cys=l-cysteinate) with [CoCl(NH3)5]2+ produced [CoIII{RhIII(aet or l-cys-N,S)3}2]3+or3−, while the reactions with Co2+ formed [CoII{RhIII(aet or l-cys-N,S)3}2]2+or4− which were oxidized to give [CoIII{RhIII (aet or l-cys-N,S)3}2]3+or3−. These complexes were optically resolved or separated by fractional crystallization or column chromatography, and characterized from their absorption, CD and 13C
Abstract Novel S-bridged CoIIIAgI3CoIII pentanuclear complexes, [Ag3{Co(aet)3}2]3+ (1) and [Ag3{Co(l-cys-N,S)3}2]3− (2), were prepared by reacting fac(S)-[Co(aet)3] (aet = 2-aminoethanethiolate) or ΔLll-fac(S)-[Co(l-cys-N,S)3]3− (l-cys = l-cysteinate) with Ag+ in a ratio of 2 : 3. The crystal structure of 1(BF4)3 was determined by X-ray crystallography. 1(BF4)3·H2O, chemical formula C12H38B3N6OF12S6Co2Ag3, crystallizes in the orthorhombic space group Pnma with a = 16.397(2), b = 13.239(2), c = 1
Abstract The reactions of newly prepared fac(S)-[IrIII(aet)3] or ΔLLL-fac(S)-[IrIII(l-cys-N,S)3]3− with Co2+, followed by the air or H2O2 oxidation, gave linear-type S-bridged trinuclear complexes, [CoIII{IrIII(aet)3}2]3+ and ΔLLLΔLLL-[CoIII{IrIII(l-cys-N,S)3}2]3−. The aet trinuclear complex was separated and optically resolved into the ΔΛ, ΔΔ, and ΛΛ isomers and the crystal structure of the ΔΛ isomer was determined by X-ray diffraction. [Co{Ir(aet)3}2](NO3)3·2H2O, chemical formula C12H40N9S6O11
Sheetlike and helical coordination polymers, {ΛL-[Ag{Co(L-cys-N,S)(en)2}](NO3)2}∞ (1) and {ΔL-[Ag{Co(L-cys-N,S)(en)2}](NO3)2}∞ (2), were obtained by treating ΛL- and ΔL-[Co(L-cys-N,S)(en)2]+ (L-cys=L-cysteinate, en=H2NCH2CH2NH2) with AgNO3 in water, respectively. Their structures are comparable to those of the β-sheet and α-helix forms of proteins. Compound 2 undergoes reversible conversion into a third compound on changing the pH of the solution.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA New Class of S-Bridged Hexanuclear Complexes with Aminoethanethiolate Ligands. Formation and Structural Characterization of [PdII2{NiII(aet)2}x{PdII(aet)2}4-x]Br4 (x = 0-4; aet = 2-Aminoethanethiolate)Takumi Konno, Kunio Yonenobu, Jinsai Hidaka, and Kenichi OkamotoCite this: Inorg. Chem. 1994, 33, 5, 861–864Publication Date (Print):March 1, 1994Publication History Published online1 May 2002Published inissue 1 March 1994https://pubs.acs.org/doi/10.102
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and properties of cage-type sulfur-bridged cobalt(III)zinc(II) polynuclear complexes. Crystal structure of spontaneously resolved [{Co(aet)3}4Zn4O]Br6 (aet = 2-aminoethanethiolate)Takumi Konno, Takayuki Nagashio, Kenichi Okamoto, and Jinsai HidakaCite this: Inorg. Chem. 1992, 31, 7, 1160–1165Publication Date (Print):April 1, 1992Publication History Published online1 May 2002Published inissue 1 April 1992https://pubs.acs.org/doi/10.1021/ic0003
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and structural characterization of spontaneously resolved [(M(aet)3)4M'4O]6+ (M = rhodium(III), iridium(III); M'4 = zinc(II)4-x cobalt(II)x; aet = 2-aminoethanethiolate): conversion of linear- to a cage-type sulfur-bridged polynuclear structureTakumi Konno, Kenichi Okamoto, and Jinsai HidakaCite this: Inorg. Chem. 1991, 30, 10, 2253–2256Publication Date (Print):May 1, 1991Publication History Published online1 May 2002Published inissue 1 May 1
Abstract An S-bridged CoIIICdII dinuclear complex molecule, [CdCl3{Co(aet)2(en)}]0 ([1]) (aet = 2–aminoethanethiolate, en = ethylenediamine), was prepared by the reaction of an S-bridged CoIIINiIICoIII trinuclear complex salt, [Ni{Co(aet)2(en)}2]Cl4, with excess CdCl2 in water. Treatment of [1] with NaNO3 in water gave an S-bridged CoIIICdIICoIII dinuclear complex salt, [CdCl{Co(aet)2(en)}2](NO3)3 ([2](NO3)3), which was further converted to a (CoIIICdIICoIII)2 hexanuclear complex salt, [Cd2Cl{Co
Abstract The reaction of fac(S)-[Rh(aet)3] with Ni2+ at room temperature gave a linear-type S-bridged RhIIINiIIRhIII trinuclear complex, [Ni{Rh(aet)3}2]2+ (1). A similar reaction of ΔLll-fac(S)-[Rh(l-cys-N,S)3]3− with Ni2+ produced the corresponding trinuclear complex with l-cys ligands, ΔLllΔLll-[Ni{Rh(l-cys-N,S)3}2]4− (ΔLllΔLll-2), retaining the ΔLll configuration of the starting complex. The crystal structure of 1(NO3)2 was determined by X-ray diffraction. [Ni{Rh(aet)3}2](NO3)2·2H2O, chemical
The reaction of fac(S)-[Rh(aet)(3)] (aet = 2-aminoethanethiolate) with 1.5 molar equiv of AgBF(4) in water gave an S-bridged pentanuclear complex, [Ag(3){Rh(aet)(3)}(2)](BF(4))(3) (1(BF(4))(3)), while the reaction with 1.2 molar equiv of AgBF(4) produced an S-bridged nonanuclear complex, [Ag(5){Rh(aet)(3)}(4)](BF(4))(5) (2(BF(4))(5)). The crystal structures of 1(BF(4))(3) and 2(BF(4))(5) were determined by X-ray crystallography: 1(BF(4))(3).H(2)O crystallizes in the orthorhombic space group Pnma
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and structure of unprecedented copper(I)-rhodium(III) CuI4RhIII4 and copper(I)-iridium(III) CuI4IrIII4 S-bridged polynuclear complexes containing .mu.2- and .mu.3-thiolato and coordinated disulfide: spontaneous reduction of copper(II) to trigonal-planar copper(I)Takumi Konno, Kenichi Okamoto, and Jinsai HidakaCite this: Inorg. Chem. 1992, 31, 19, 3875–3876Publication Date (Print):September 1, 1992Publication History Published online1 May 2002
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