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Assembled Transition Metal Cluster Complexes with Open Shell as Functional Materials

Research Project

Project/Area Number 07555573
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 工業物理化学
Research InstitutionGIFU UNIVERSITY

Principal Investigator

KAWAMURA Takashi  Gifu University, Faculty of Engineering, Professor, 工学部, 教授 (40026125)

Co-Investigator(Kenkyū-buntansha) EBIHARA Masahiro  Gifu University, Faculty of Engineering, Research Associate, 工学部, 助手 (80201961)
TSUJI Yasushi  Gifu University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (30144330)
Project Period (FY) 1995 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 1997: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1996: ¥1,400,000 (Direct Cost: ¥1,400,000)
Keywordscluster complex / ionic radical / magnetism / crystal structure / odd-electron distribution / rhodium / aromatic ligand / metal-metal bond / 不対電子軌道 / 共役
Research Abstract

In transition metal dimetal complexes as dirhodium one with pi-conjugated bridging ligands, formation of novel electronic system which was constructed by ligand pi-systems interacting through metal d-orbitals is observed. (1) Cationic radical salts were generated by oxidation of rhodium dimer complexes with axial phospfine ligands. X-ray structure analysis of the salts were carried out. The ionization induced elongation of Rh-Rh bond by 0.05 and shortening of Rh-P bond by 0.12* , showing enhanced delocalization of the Rh-Rh bonding orbital onto the phosphine ligands. (2) Magnetic susceptibility data of a cationic radical salt of rhodium dimer complex with methylhydroxypyridine ligands indicated that spin-spin interaction was diamagnetical (10 cm^<-1>). (3) Electronic structure of cationic radical of rhodium dimer complexes with various ligands were calculated by DFT method. The symmetry of odd-electron orbital and the extent of delocalization onto ligand depend on the ligands. (4) Crys … More tal structure, electronic structure, magnetic susceptibility, and electric conductance of cationic radical salts of dirhodium complexes with large pi-conjugated bridging ligands, 2-hydroxyquinoline fits analogues, were investigated. 1) The odd-electron in the Rh-Rh delta^<**>-orbital is delocalized onto pi-orbitals of the four bridging ligands to the extent of 10%. 2) The delocalization of the odd-electron on the bridging ligand is not onto the HOMO of the ligand, but the orbital given by a linear combination of the HOMO and the LUMO.3) Intermolecular ligand-ligand (C-C) short contact was observed in the crystals of cationic radical salts with various counter anion and crystalline solvent. Magnetic susceptibility of the radical cation salts were measured. Magnetic susceptibility obeys Curie law with diamagnetic interaction at low temperature for the crystals with short C-C contacts. (5) High nuclearity cluster complexes of group 10 and 11 were prepared and their structure were determined. (6) Structure and isomerization of a reaction intermediate in Pt- and Pd-catalized stannylation reaction were studied. Less

Report

(4 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • 1995 Annual Research Report
  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] 海老原 昌弘: "Mixed Metal Complexes of Group 10 and 11 Elements. The Structure and Properties of [M (mnt)_2{Ag(PR_3)}_3] (M=Ni、Pd、Pt : mnt2-=maleonitriledithilate)" Inorg.Chim.Acta. 231. 35-43 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 所 健児: "(CuX)_n Helical Chains in [Pt(S2CNEt2)2Cu2X2] (X=Br,Cl)" Acta Crystallog.C51. 2010-2013 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 大洞 康嗣: "Structure and Fluxional Behavior of cis-Bis (Stannyul) bis (phosphine) platinum : Oxidative Addition of Organodistannane to Platinum (0) Complex" J.Am.Chem.Soc.118. 10922-10923 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 辻 康之: "Structure and Facile Unimolecular Twist-Rotation of cis-Bis (silyl) bis (phosphine) platinum and cis-Bis (stannyl) bis (phosphine) palladium Complexes." Organometall.(印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Masahiro Ebihara: "Mixed Metal Complexes of Group 10 and 11 Elements. The Structure and Properties of [M(mnt)_2{Ag(PR_3)}_2] (M=Ni, Pd, Pt ; mnt2-=maleonitriledithilate)" Inorg.Chim.Acta. 231. 35-43 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Kenji Tokoro: "(CuX)_n Helical Chains in [Pt(S_2CNEt_2)_2Cu_2X_2] (X=Br, Cl)" Acta Crystallog.C51. 2010-2013 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Yasushi Obora: "Structure and Fluxional Behavior of cis-Bis (Stannyul) bis (phosphine) platinum : Oxidative Addition of Organodistannane to Platinum (0) Complex" J.Am.Chem.Soc.118. 10922-10923 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Yasushi Tsuji: "Structure and Facile Unimolecular Twist-Rotation of cis-Bis (silyl) bis (phosphine) platinum and cis-Bis (stannyl) bis (phosphine) palladium Complexes" Organometall. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.ケツゴウ辻康之:

    • Related Report
      1997 Annual Research Report
  • [Publications] "Structure and Facile Unimolecular Twist-Rotation of cis-Bis(silyl)bis(phosphine)platinum and cis-Bis(stannyl)bis(phosphine)palladium Complexes." Organometall.(印刷中).

    • Related Report
      1997 Annual Research Report
  • [Publications] 大洞康嗣: "Structure and Fluxional Behavior of cis-Bis (Stannyul) bis (phosphine) platinum : Oxidative Addition of Organodistannaneto Platinum (0) Complex" J.Am.CHem.Soc.,118,10922-10923 (1996).

    • Related Report
      1996 Annual Research Report
  • [Publications] 海老原昌弘: "Mixed Metal Complexes of Group 10 and 11 Elements. The Structure and Properties of [M(mnt)_2{Ag(PR_3)}_2](M=Ni, Pd, Pt; mnt^<2->=maleonitriledithilate)" Inorg. Chim. Acta. 231. 35-43 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 所健児: "(CuX)_n Helical Chains in [Pt(S_2CNEt_2)_2Cu_2X_2] (X=Br, Cl)" Acta Cryst.C51. 2010-2013 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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