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Chemistry of Transition Metal Supramolecules

Research Project

Project/Area Number 07044051
Research Category

Grant-in-Aid for international Scientific Research

Allocation TypeSingle-year Grants
SectionJoint Research
Research InstitutionTohoku University

Principal Investigator

OGINO Hiroshi  Graduate School of Science, Tohoku University, Professor, 大学院・理学研究科, 教授 (00004292)

Co-Investigator(Kenkyū-buntansha) BRAUNSTEIN P  Faculte de Chimie, Universite Louis Pasteur, パスツール大学・化学教室, 教授
SAUVAGE J.P  Faculte de Chimie, Universite Louis Pasteur, パスツール大学・化学教室, 教授
INOMATA Shinji  Graduate School of Science, Tohoku University, 大学院・理学研究科, 助手 (50241518)
UENO Keiji  Graduate School of Science, Tohoku University, 大学院・理学研究科, 助手 (20203458)
TOBITA Hiromi  Graduate School of Science, Tohoku University, 大学院・理学研究科, 助教授 (30180160)
SAUVAGE J.P.  ルイ, パスツール大学・化学教室, 教授
BRANUSTEIN P  ルイ, パスツール大学・化学教室, 教授
Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 1996: ¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1995: ¥1,900,000 (Direct Cost: ¥1,900,000)
KeywordsTransition metal / Cluster / Supramolecule / Silicon / Germanium / Phosphorus / Chalcogenide
Research Abstract

Several new diiron and iron-ruthenium complexes in which two metal units in different environments are bridged by a phosphido ligand have been synthesized. These complexes were found to react with various alkynes, dihydrosilanes, and hydrodisilanes under mild conditions to give the complexes in which these small molecules were incorporated as parts of newly formed ligands.
The primary and secondary germanes were found to react with Cp'Fe (CO)_2SiMe_3 (Cp'=eta^5-C_5H_5, eta^5-C_5Me_5) upon UV irradiation to give mono-and bis (germylene) -bridged complexes. When the primary germane and the eta^5-C_5Me_5 complex were photolyzed, the unprecedented dinuclear complex with two Ge-H-Fe 3 center-2 electron bonds was also formed.
New systematic synthesis of mixed-ligand and also mixed-metal transition metal-sulfur trinuclear and tetranuclear clusters has been achieved starting from sulfido-or disulfido-bridged diiron complexes.
The facile 1,3-migration of substituents on a silylene-transition metal-silyl linkage (Si=M-Si) was confirmed for the first time by generating base-free silyl (silylene) complexes from base-stabilized ones on heating.
The silyltetrakis (phosphine) iridium (I) complex was synthesized for the first time and it was found that this complex generates a 16-electron Ir (I) species by dissociation of a phosphine ligand at room temperature. This complex catalyzes the intramolecular rearrangement of substituents in hydrodisilanes to lead the isomerization. Starting from the same complex, the synthesis of the first silyl (silylene) complex of group 9 element has been achieved.

Report

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

    (29 results)

All Other

All Publications (29 results)

  • [Publications] Amr El-Maradny: "Photoreactions of silyliron (II) complexes Cp'Fe (CO)_2SiMe_3 (Cp'=η^5-C_5H_5,η^5-C_5Me_5) with di-p-tolylgermane (p-Tol)_2GeH_2" Chem.Lett.1996. 83-84 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Mikiya Yamada: "Isolation and structural characterization of complexes formed in the reactions of [{C_5H_4 (SiMe_3)}_2Fe_2 (CO)_4] and [{1,3-C_5H_3(SiMe_3)_2}_2Fe_2 (CO)_4] with elemental sulfur" Bull.Chem.Soc.Jpn.69. 861-867 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Keiji Ueno: "Synthesis of a donor-stabilized silyl (silylene) iron complex. Direct observation of 1,3-methyl migration from silyl to silylene ligands" Chem.Lett.1996. 459-460 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Masaaki Okazaki: "Generation of hydrido (silylene) iridium (I) complex via [1,2] H shift from the silicon atom to the iridium (I) metal center" Chem.Lett.1996. 477-478 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Masaaki Okazaki: "Synthesis and structure of the {(2-phosphinoethyl)-silyl} tris (tertiary phosphine) iridium (I) complex Ir (η^2-Me_2Si (CH_2)_2PPh_2} (PMe_3)_3" Organometallics. 15. 2790-2793 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Amr El-Maradny: "Photoreaction of silyliron (II) complex Cp^*Fe (CO)_2SiMe_3 (Cp^*=η^5-C_5Me_5) in the presence of p-tolygermane" Organometallics. 15. 4954-4958 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Amr El-Maradny: "Photoreactions of silyliron (II) complexes Cp'Fe (CO)_2SiMe_3 (Cp'=eta^5-C_5H_5, eta^5-C_5Me_5) with di-p-tolylgermane (p-Tol)_2GeH_2" Chem.Lett.1996. 83-84 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Mikiya Yamada: "Isolation and structural characterization of complexes formed in the reactions of [{C_5H_4 (SiMe_3)}_2Fe_2 (CO)_4] and [{1,3-C_5H_3 (SiMe_3)_2}_2Fe_2 (CO)_4] with elemental sulfur" Bull.Chem.Soc.Jpn.69. 861-867 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Keiji Ueno: "Synthesis of a donor-stabilized silyl (silylene) iron complex. Direct observation of 1,3-methyl migration from silyl to silylene ligands" Chem.Lett.1996. 459-460 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Masaki Okazaki: "Generation of hydrido (silylene) iridium (I) complex via [1,2] H shift from the silicon atom to the iridium (I) metal center" Chem.Lett.1996. 477-478 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Masaki Okazaki: "Synthesis and structure of the {(2-phosphinoethyl) -silyl} tris (tertiary phosphine) iridium (I) complex Ir {eta^2-Me_2Si (CH_2)_2 PPh_2} (PMe_3)_3" Organometallics. 15. 2790-2793 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Amr El-Maradny: "Photoreaction of silyliron (II) complex Cp^<**>Fe (CO)_2 SiMe_3 (Cp^<**>=eta^5-C_5Me_5) in the presence of p-tolylgermane" Organometallics. 15. 4954-4958 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Amr El-Maradny: "Photoreactions of silyliron (II) complexes Cp′Fe(CO)_2SiMe_3(Cp′=η^5-C_5H_5,η^5-C_5Me_5) with di-ptolygermane (p-Tol)_2GeH_2" Chem. Lett.1996. 83-84 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Mikiya Yamada: "Isolation and structural characterization of complexes formed in the reactions of [{C_5H_4(SiMe_3)}Fe_2(CO)_4}] and [{1,3-C_5H_3(SiMe_3)_2}_2Fe_2(CO)_4] with elemental sulfur" Bull. Chem. Soc. Jpn.69. 861-867 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Keiji Ueno: "Synthesis of a donor-stabilized sily (silylene) iron complex. Direct observation of 1,3-methyl migration from silyl to silylene ligands" Chem. Lett.1996. 459-460 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Massaki Okazaki: "Generation of hydrido (silylene) iridium (I) complex via [1,2] H shift from the silicon atom to the iridium (I) metal center" Chem. Lett.1996. 477-478 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Masaaki Okazaki: "Synthesis and structure of the {(2-phosphinoethyl)-silyl} tris (tertiary phosphine) iridium (I) complex Ir {η^2-Me_2Si(CH_2)_2PPh_2}(PMe_3)_3" Organometallics. 15. 2790-2793 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Amr El-Maradny: "Photoreaction of silyliron (II) complex Cp^*Fe(CO)_2SiMe_3(Cp^*=η^5-C_5Me_5) in the presence of p-tolylgermane" Organometallics. 15. 4954-4958 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] A. El-Maradny: "Photoreactions of silyliron (II) complexes Cp' Fe(CO)_2SiMe_3(Cp'=η-C_5H_5,η-C_5Me_5) with dip-tolylgermane (p-Tol)_2GeH_2" Chemistry Letters. 1996. 83-84 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] H. Kobayashi: "Synthesis of the cationic silyleneiron complex [CpFe(CO)_2=SiMe{2-(Me_2NCH_2)C_6H_4}]PF_6 by hydride abstraction from a (hydrosilyl) iron complex with Ph_3CPF_6" Organometallics. 14. 5490-5492 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M. Okazaki: "Light and heat-induced geometric isomerization of chloro (hydro) iridium (III) complex containing a (2-phosphinoethyl) silyl chelate ligand" Chemistry Letters. 1995. 1005-1006 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] H. Hashimoto: "Redistribution reactions of hydrosilanes mediated by the unsymmetrical and homometallic phosphido-bridged complex (η-C_5Me_5)Fe_2(CO)_4(μ-CO)(μ-PPh_2)" Journal of the Organometallic Chemistry. 499. 205-211 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] H. Tobita: "Silylene-bridged dinuclear complexes having a triplet ground state: Photochemical synthesis and structural characterization of Cp_2Fe_2(μ-CO)_2(μ-SiR_2)" Journal of the American Chemical Society. 117. 7013-7014 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] K. Ueno: "Kinetic study of interconversion between two geometrical isomers of the methoxy-bridged bis (silylene) iron complex" Bulletin of the Chemical Society of Japan. 68. 1955-1958 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 飛田 博実: "低原子価ケイ素およびゲルマニウムを配位した遷移金属錯体の合成と性質" 有機合成化学協会誌. 53. 530-540 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S. Inomata: "Synthesis and structure of a diiron complex with a highly bent dithiolene bridged, Cp^*_2Fe_2(CO){S_2C_2(CO_2Me)_2}(Cp^*=η-C_5Me_5)" Organometallics. 14. 5490-5492 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] K. Hashidzume: "Electrochemistry of octamethl[3]ruthenocenophane: Syntesis and structure of the first dicationic derivative of ruthenocene" Organometallics. 14. 1187-1194 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] A.Harriman: "Multistep electron transfer between porphyrin modules assembled around a ruthenium center" Journal of the American Chemical Society. 117. 9461-9472 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Knorr: "Novel CO-induced silyl migration in heterobimetallic iron-palladium methyl complexes leading to μ-siloxycarbene complexes" Organometallics. 14. 4910-4919 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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