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Stereochemistry, Photochemistry, and Magnetism of Sulfur-Bridged Metal-Cluster Complexes

Research Project

Project/Area Number 08454215
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionOkayama University of Science

Principal Investigator

SHIBAHARA Takashi  Dept.of Chemistry Okayama university of Science Professor, 理学部, 教授 (30122386)

Co-Investigator(Kenkyū-buntansha) SAKANE Genta  Dept.of Chemistry Okayama University of Science Lecturer, 理学部, 講師 (90278911)
Project Period (FY) 1996 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥7,900,000 (Direct Cost: ¥7,900,000)
Fiscal Year 1998: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1997: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1996: ¥4,500,000 (Direct Cost: ¥4,500,000)
Keywordsmolybdenum / tungsten / sulfur-bridge / metalcluster / complex / photochromism / photochemistry / sterochemistry / カドミウム / ニッケル / アセチレン / イミノ二酢酸 / 異性化 / クラスター / 光学活性 / ガリウム / 磁性 / 分子軌道計算
Research Abstract

This research has pursued mainly the versatile nature of sulfur-bridged tri- or tetra-nuclear molybdenum and tungsten cluster complexes, and has paid attention not only to metal concerning substitution and redox reaction, but also to the reactivity of bridging sulfur.
Through the reaction of sulfur-bridged incomplete cubane-type cluster with acetylene, cluster complexes having sulfur-carbon bonds were obtained and characterized, and their X-ray structures were determined. In addition it was made clear that the reactivity of bridging sulfurs of sulfur/oxygen-bridged tungsten clusters is influenced by ligands. The finding of the sulfur-carbon bond formation induced us to find novel molybdenum, tungsten, and chromium compounds, some of which show photochromism.
Metal incorporation reaction, which is one of our research theme for years, has also been developed : novel molybdenum gallium, molybdenum-antimony, and molybdenum-cadmium clusters have been synthesized and characterized.
A sulfur-bridged cubane-type nitrilotriacetato tungsten-nickel cluster has been synthesized, from which a hydrazine coordinated complex was isolated and characterized.
Deprotonated ethylenediamine clusters were obtained from sulfur/oxygen bridged incomplete cubane-type clusters. In addition, four isomers of sulfur-bridged incomplete cubane-type iminodiacetato molybdenum clusters have been isolated, three structures of them were determined by X-ray crystallography, and isomerization among the four isomers was detected.

Report

(4 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • 1996 Annual Research Report

Research Products

(24 results)

All Other

All Publications (24 results)

  • [Publications] T. Shibahara et al.: "Sulfur-Bridged Cubane-Type Holybdenm-Gallium Clusters with Mo_3Go_1S_4^<n+>‥‥" Inorg, Chem,. 36. 1702-1706 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T. Shibahara et al.: "Photochromism of Dinuclear Molybdenum Complexes with Disulfur and‥‥" Chemistry Letters,. 445-446 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] R. Miyamoto, S. Kawata, M. Iwazumi, H. Akashi, and T. Shibahara: "EPR Studies of the Mixed-Metal Cubane-Type Complex Having a [Mo_3CuS_4(H_2O)_<10>]^<4+>Core" Inorg. Chem,. 36. 542-546 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H. Akashi, N. Uryu and T. Shibahara: "Magnetic susceptibility aralysts of mixed metal cubane-type cluster comlexes, [tetra‥‥" Inorg. Chem, Acta,. 261. 53-57 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H. Aikoh, M. Yamate, M. Takahashi, and T. Shibahara: "Petermination of Mercury Levels In Biological Samples Using the Incomplete Cubane-Type‥‥" Physiol. Chem. Phys. & Med. NMR. 29. 109-122 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Sasaki, G. Sakane, T. Ouchi, and T. Shibahara: "Synthesis, Structure, and ^<31>PNMR of Sulfur/Oxygen-Bridged Incomplete Cubane-Type Molybden" Journal of Cluster Sclence,. 9. 25-43 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Shibahara, S.Kobayashi, N.Tsuji, G.Sakane, and M.Fukuhara: "Sulfur-Bridged Cubane-Type Molybdenum-Gallium Clusters with Mo_3GaS_4^<n+> (n=5,6) cores. X-ray Structures of [Mo_3GaS_4(H_2O)_<12>](CH_3C_6H_4SO_3)_5・14H_2O and [Mo_3GaS_4(H_2O)_<12>](CH_3C_6H_4SO_3)_6・17H_2O" Inorg.Chem.36. 1702-1706 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Shibahara, N.Iwai, M.Sasaki, and G.Sakane: "Photochromism of Dinuclear Molybdenum Complexes with Disulfur and Ethylene-1,2-dithiolate Ligands." Chemistry Letters. 445-446 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] R.Miyamoto, S.Kawata, M.Iwaizumi, H.Akashi, and T.Shibahara: "EPR Studies of the Mixed-Metal Cubane-Type Complex Having a [Mo_3CuS_4(H_2O)_<10>]^<4+> Core." Inorg.Chem.36. 542-546 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Akashi, N.Uryu, and T.Shibahara: "Magnetic susceptibility analysis of mixed metal cubane-type cluster complexes, [tetra-mu_3-thiotris {tri (aqua) molybdenum} aquairon] (4+) paratoluensulfonate heptahydrate and [tetra-mu_3-thiotris {tri (aqua) molybdenum} aquanickel] (4+) paratoluensulfonate heptahydrate" Inorg.Chim.Acta. 261. 53-57 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Aikoh, M.Yamate, M.Takahashi, and T.Shibahara: "Determination of Mercury Levels in Biological Samples Using the Incomplete Cubane-Type Sulfur-Bridged Nitrilotriacetato Molybdenum Complex by a Spectrophotometer" Physiol.Chem.Phys.& Med.NMR. 29. 109-122 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Sasaki, G.Sakane, T.Ouchi, and T.Shibahara: "Synthesis, Structure, and ^<31>P NMR of Sulfur/Oxygen-Bridged Incomplete Cubane-Type Molybdenum and Tungsten Clusters with Triphenylphosphine Ligands" J.Cluster Science. 9. 25-43 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] G.Sakane, K.Hashimoto, M.Takahashi, M.Takeda, and T.Shibahara: "Sulfur-Bridged Sandwich Cubane-Type Molybdenum-Antimony Cluster. Synthesis, X-ray Structure, and ^<121>Sb MOssbauer Spectra of [(H_2O)_9Mo_3S_4SbS_4Mo_3(H_2O)_9](CH_3C_6H_4SO_3)_8・24H_2O" Inorg.Chem.37. 4231-4234 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Akashi and T.i Shibahara: "Preparation and characterization of twin-cubane-type cluster with molybdenum-copper-sulfur cores. X-ray structure determination of [{(NH_3)_6(H_2O)(OH)Mo_3CuS_4(O)}_2]Cl_4・8H_2O" Inorg.Chim.Acta. 282. 50-54 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Shibahara et al.: "Sulfur-Bridged Cubane-Type Holybdenum-Gallium clusters with Mo_3Ga_1S_4^<n+>・・・・" Inorg.Chem.36. 1702-1706 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Shibahara et al.: "Photochromism of Dinuclear Molybdenum Complexes with Disulfurand・・・・" Chemistry Letters.445-446 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] R.Miyamoto,S.Kawata,M.Iwaizumi,H.Akashi,and T.shibahara: "EPR Studies of the Hixed-Metal Cubane-Type Complex thving a [Mo_3CuS_4(H_2O)_<10>]^<4+>Coto" Inorg.chem,. 36. 542-546 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Akashi,N.Uryu and T.Shibahara: "Magnetic susceptibility analysis of mixed metal cubane-type cluster Oomplexes,[tetra-・・・・" Inorg,chem,Acta,. 261. 53-57 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Aikoh,M.Yamate,M.Takahashi,and T.Shibahara: "Retermination of Mercury Levels in Biological Samples Using the Incomplete Cubane-Type・・・・" Physiol.chem.phys. & Med.NMR.29. 109-122 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Sasaki,G.Sakane,T.Ouchi,and T.Shibahara: "Synthesis,Structure,and ^<31>PNMR of Sulfur/Oxygen-Bridged Incomplete Cubane-Type Habbdenum・・・" Jeurnal of cluster Science,. 9. 25-43 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takashi Shibahara: "Sulfur-Bridged Cubane-Type Molybdenum-Gallium Clusters…" Inorganic chemistry. 36・8. 1702-1706 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takashi Shibahara: "Photoch romism of Dinuclear Molybdenum Complexes with…" Chemistry Letters. 5. 445-446 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Hiromi Aikoh: "Determination of Mercury Levels in Biological Samples Using…" Physiol. Chem. Phys. & Med. NMR. 29. 109-122 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 柴原隆志他4名: "Sulfur-Bridged Cubane-Type Molybdenum-Gallium Clusters" Inorganic Chemistry. (4月発行予定). (1997)

    • Related Report
      1996 Annual Research Report

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Published: 1996-03-31   Modified: 2016-04-21  

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