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ヘテロ遷移金属錯体の金属間共同作用の発現と応用

Research Project

Project/Area Number 12042225
Research Category

Grant-in-Aid for Scientific Research on Priority Areas (A)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionTokyo University of Agriculture and Technology

Principal Investigator

小宮 三四郎  東京農工大学, 工学部, 教授 (00111667)

Co-Investigator(Kenkyū-buntansha) 小峰 伸之  東京農工大学, 工学部, 助手 (90302918)
平野 雅文  東京農工大学, 工学部, 助教授 (70251585)
Project Period (FY) 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2001: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 2000: ¥1,900,000 (Direct Cost: ¥1,900,000)
Keywordsヘテロ二核錯体 / パラジウム / コバルト / 一酸化炭素挿入反応 / 共同効果 / 一酸化炭素
Research Abstract

本研究では、触媒反応と密接に関連すそ10族遷移金属と6,7,8族遷移金属間結合を有するヘテロ二核錯体を合成単離し、その化学反応性や安定性を検討することにより、二つ以上の遷移金属がもたらす共同効果の本質を解明すること、およびこれらの共同効果を基礎としたより効率的で完全な分子変換法を開拓することを目的とする。
メチルパラジウム-コバルト二核錯体(dppe)MePd-Co(CO)_4と一酸化炭素との反応が、対応する単核錯体であるPdMeCl(dppe)の場合と比べて、40倍程度速く進行し、Pd-Me間に一酸化炭素か挿入したアセチル錯体(dppe)AcPd-Co(CO)_4を与えるという極めて顕著な二核錯体による反応促進効果を見出した。^<13>COを用いた反応により、この一酸化炭素挿入反応において、Pd-Me間に挿入するのは添加した^<13>COではなく、コバルト上のCOであることも明らかにした。また、名古屋大学の古賀教授との共同研究による理論計算の結果から、本反応ではPd上のメチル基が一旦Co上に移動し、Co上で炭素-金属間にCOが挿入したのち、再びPd上に移動することで生成物であるアセチルコバルト錯体を与えることをも明らかにした。

Report

(2 results)
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (10 results)

All Other

All Publications (10 results)

  • [Publications] A.Fukuoka, S.Fukagawa, M.Hirano, N.Koga, S.Komiya: "Enhancement of CO Insertion into a Pd-C Bond in a Pd-Co Heterodinuclear Complex"Organometallics. 20(10). 2065-2075 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Kanaya, N.Komine, M.Hirano, S.Komiya: "Preferential bond activation of sp^3 C-H over sp^2C-H in α,β-unsaturated carboxylic acids by ruthenium complex"Chemistry Letters. (12). 1284-1285 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Komiya, M.Ikuine, N.Komine, M.Hirano: "Synthesis and Reactions of Water-soluble Diorganoplatinum(II) Complexes"Chemistry Letters. (1). 72-73 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Komiya, et al: "Enhancement of CO insertion into Pd-C bond on Pd-Co hetrerodinuclear complexes"Organometallics. 20(in press). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Komiya, et al: "Oxidative Addition of Organocobalt (I) and-molybdenum (II) Complexes to Palladium (0) Complex to Give Heterodinuclear Organometallic Complexex"Organometallics. 19. 5251-5253 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Komiya, et al: "Stereoselective Insertion Reactions of Thiiranes into Pt-Mn (or Re) Bond in Organoplatinum-Manganese or-Rhenium Heterodinuclear Complexes as Intermediates toward Desulfurization"Journal of American Chemical Society. 122. 171-172 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Komiya, et al: "Synthesis of Hydridoplatinum-Molybdenum (or Tungsten) Heterodinuclear Complexes by βHydrido Elimination of (dppe)EtPt-WCp(CO)_3.Selective Hydride Transfer from Pt to W"Journal of Moecular Catalyst. 159. 63-70 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Komiya, et al: "Successive O-H and sp^3 C-H Bond Activation of Ortho-substituted Phenols by a Ruthenium (0) Complex"Journal of Organometallic Chemistry. 607. 18-26 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Komiya, et al: "Addition of N-Bonded Enolato Ligands to Acrylonitrile in Iron and Ruthenium Complexes"Chemical Communication. 1679-1680 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] N.Komine,H.Hoh,M.Hirano,S.Komiya: "Oxidative Addition of Organocobalt (I) and-molybdenum (II) Complexes to Palladium (0) Complex to Give Heterodinuclear Organometallic Complexes"Organometallics. 19. 5251-5253 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 2000-04-01   Modified: 2018-03-28  

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