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Capture and Elimination of Reactive Intermediates on the Metalladichalcogenolene Rings

Research Project

Project/Area Number 09640673
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionSophia University

Principal Investigator

KAJITANI Masatsugu  Sophia UniversiLy, Faculty of Science and Technology, 理工学部, 助教授 (00053702)

Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 1998: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1997: ¥2,100,000 (Direct Cost: ¥2,100,000)
Keywordsmetalladichalcogenolene / nitrene / aromaticity / alkylidene adduct / bond cleavage / imido adduct / OTTLE / electrochemical behavior / アルキリデン / コバルタジチオレン錯体 / イミド / 付加反応 / アジド化合物 / ジアゾ化合物 / X-線構造解析
Research Abstract

The metalladithiolene ring in [CpCo(SィイD22ィエD2CィイD22ィエD2XY)]-type dithiolatocobalt complexes show a variety of reactivities due to unsaturation and due to aromaticity. The rings undergo the addition reactions which are ascribed to the unsaturation (multi bond plicity) between the metal and sulfur atoms in the metalladithiolene rings. Dimethyl acetylenedicarboxylate, quadricyclanc, diazo compounds, and azide compounds which were able to use as precursors of reactive intermediates bridge between metal and sulfur to form alkene-, norbornene-, alkylidene-, and imido-bridged adducts.
In this work, our attention was focused especially on alkylidene and imido-bridged adducts from the standpoint of capture and elimination of reactive intermediates on the metalladichalcogenolene rings. They further react with Lewis bases and protic acids, resulting in the opening of the three-membered rings in adducts to afford the corresponding three-component adducts. Interestingly, the bond cleaved is dependent on the attacking reagents and on the structures of the bridging groups.
We investigated in detail the electrochemical behavior of alkylidene- and imido-bridged adducts and their three-component adducts, together with their photochemical behavior and their thermal activation with chemical reagents. As a topic, the reaction of the sulfonylimido-bridged addut with triphenylphosphine resulted in the migration of imido group to the cyclopentadienyl ring. From a cross over experiment, the rearrangement has been concluded to be an intermolecular reaction, suggesting the participation of nitrene species.

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (34 results)

All Other

All Publications (34 results)

  • [Publications] C. Takayama,: "Ractions of [CpCo(dmit)](Cp : C_5H_5dmit : C_5S_5)wifth Tetracyanoethylene Oxide (TCNEO) : Synthesis of a New Complex Having Novel Planar Ligand and Its Electrochemikal Behavior"Organometallics,. 17. 4341-4343 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T. Akiyama,: "Structure and Electrochemical Properties Dirctly Bound Dinuclear Cobaltadithiolene Complexes. Substituent Effect on Reduction Potentials and Mixed-Valence States"Bull. Chem. Soc. Jpn.. 71. 2351-2358 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T. Harada.: "(n^5-Cyclopentadienyl) (Halo or Acido) (Substituted 1-Methyl-kS-ethylene-2- thiolato) cobalt(III) : Formation, Stereoisomers, and Isomerization"Bull. Chem. Soc. Jpn.,. 71. 2645-2653 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] C. Takayama,: "Structur and elecrochemical behavior of alkylidene-bridfed metalladithiolene complexs(metals : cobalt and rhodium) : bond cleavae of alkylidenemoieties by electrochemical redox rcactions"J. Organomet. Chem.,. 563. 161-171 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T. Sugiyama,: "Thermal and Photochemical Formation of Dinuclear Molybdenadithiolene Comlexes in One-Pot Reactions amoung [(Cp)_2Mo_2(CO)_6] Elementaol Sulfur and Dimethyl Acethylene-dicaboxylae"Chem. Lett.,. 1998. 501-502 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] C. Takayama,: "Reactions of Tetacyanoethylene Oxidle(TCNEO) with Cobaltadithiolene Complexes"Chtm. Left.,. 1998. 241-242 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M. Kajitani,: "Crystal Structur of[Bid(1,2-diphenylphosphino)- ehane] (maleonitriledithiolato)-nickel(II)"Anal. Sciences,. 13. 873-874 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A. Sugimori,: "Ionic and Radical Substitution in Cobaltadithiolene Ring by Dibenzoyl Peroxide"Chem. Lett.,. 1997. 807-808 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] C. Takayama,: "Structural Changes Induced by Electron-Transfer Reactions. Isomerization of Alkylidene Moiety by the Reversible Metal-Carbon Bond Clcavage in the Alkylidene-Bridged Cobaltadithiolene"Organometallics,. 16. 3498-3503 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M. Kajitani,: "Reactions of Cobaltadithiolenes with Gemanorbomadiene-Formation and Structure of Unique Binuclear Cobalt Complexes Containing a Bridging Dimethylgermylene Moiety"Organometallics,. 16. 2213-2215 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A. Sugimori,: "Formation of Cobaltadithiolene in a One-Pot Reaction amoung [Co(Cp)(CO)_2],α β-Unsatsurated Carbonyls, and Elemental Sulfur"Chem. Lett.,. 1997. 513-514 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] C. Takayama: "Ractions of [CpCo(dmit)] (Cp : CィイD25ィエD2HィイD25ィエD2 dmit : CィイD23ィエD2SィイD25ィエD2) with Tetracyanoethylene Oxide (TCNEO) : Synthesis of a New Complex Having a Novel Planar Ligand and Its Electrochemical Behavior"Organometallics. 17. 4341-4343 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T. Akiyama: "Structure and Electrochemical Properties Directly Bound Dinuclear Cobaltadithiolene Complexes. Substituent Effect on Reduction Potentials and Mixed-Valence States"Bull. Cizem. Soc. Jpn. 71. 2351-2358 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T. Harada: "(ηィイD15ィエD1-Cyclopentadienyl)(Halo or Acido)(Substituted 1-Methyl-κS-ethylene-2-thiolato)cobalt(III) : Formation, Stereoisomers, and Isomeriz_ation"Bull. Cizem. Soc. Jpn. 71. 2645-2653 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] C. Takayama: "Structure and elecrochemical behavior of alkylidene-bridged metalladithiolene complexs (metals : cobalt and rhodium) : bond cleavae of alkylidenemoieties by electrochemical redox reactions"J. Organomet. Cherm. 563. 161-171 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T. Sugiyama: "Thermal and Photochemical Formation of Dinuclear Molybdenadithiolene Complexes in One-Pot Reactions amoung [(Cp)ィイD22ィエD2MoィイD22ィエD2(CO)ィイD26ィエD2], Elemental Sulfur and Dimethyl Acetylene-dicaboxylae"Chem Lett. 501-502 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] C. Takayama: "Reactions of Tetracyanoethylene Oxide (TCNEO) with Cobaltadithiolene Complexes"Chem Lett. 241-242 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M. Kajitani: "Crystal Structure of[Bis(1,2-diphenylphosphino)-ethane](maleonitriledithiolato)nickel(II) [Ni(dppe)(mnt)]-CHィイD22ィエD2ClィイD22ィエD2"Anal. Sciences. 13. 873-874 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A. Sugimori: "Ionic and Radical Substitution in Cobaltadithiolene Ring by Dibenzoyl Peroxide"Chem Lett. 807-808 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] C. Takayama: "Structural Changes Induced by Electron-Transfer Reactions. Isomerization of Alkylidene Moiety by the Reversible Metal-Carbon Bond Cleavage in the Alkylidene-Bridged Cobaltadithiolene Complex"Organometallics. 16. 3498-3503 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M. Kajitani: "Reactions of Cobaltadithiolenes with Germanorbornadiene-Formation and Structure of Unique Binuclear Cobalt Complexes Containing a Bridging Dimethylgermylene Moiety"Organometallics. 16. 2213-2215 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A. Sugimori: "Formation of Cobaltadithiolene in a One-Pot Reaction amoung [Co(Cp)(CO)ィイD22ィエD2], α,β-Unsatsurated Carbonyls, and Elemental Sulfur"Chem Lett. 513-514 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] C. Takayama: "Reactions of Tetracyanoethylene Oxide (TCNEO) with Cobaltadithiolene Complexes," Chem. Lett.241-242 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T. Sugiyama: "Thermal and Photochemical Formation of Dinuclear Molybdenadithiolene Complexes in One-Pot Reactions amoung [ (Cp) _2Mo_2 (CO) _6] , Elemental Sulfur and Dimethyl Acetylenedicaboxylate." Chem. Lett.501-502 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] C. Takayama: "Structure and elecrochemical behavior of alkylidene-bridged metalladithiolene Complexes (metals : cobalt and rhodium) : bond cleavae of alkylidenemoieties by electrochemical redox reactions," J. Organoment. Chem.563. 161-171 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] C. Takayama: "Reactions of [CpCo (dmit) ] (Cp : C_5H_5) with Tetracyanoethylene Oxide (TCNEO) : Synthesis of a New Complex Having a Novel Planar Ligand and Its Electrochemical Behavior," Organometallics. 17. 4341-4343 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T. Akiyama: "Structure and Electrochemical Properties Directly Bound Dinuclear Cobaltadithiolene Complexes. Substituent Effect on Reduction Potentials and Mixed-Valence States," Bull. Chem. Soc. Jpn. 71. 2351-2358 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T. Harada: "(η^5-Cyclopetadienyl) (Halo or Acido) (Substitutd 1-Methyltjio-κS-ethylene-2-thiolato) cobal (III) : Formation, Stereoisomers, and Isoerization" Bull. Chem. Soc. Jpn. 71. 2645-2653 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Kajitani, S.Adachi et al.: "Reactions of Cobaltadithiolenes with Germanorbornadiene-Formation and Structure of Unique Binuclear Cobalt Complexes Containing a Bridging Dimethylgermylene Moiety" Organometallics. 16. 2213-2215 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] A.Sugimori, M.Kajitani et al.: "Formation of Cobaltadithiolene in a One-Pot Reaction amoung[Co(Cp)(CO)_2],α,β-Unsatsurated Carbonyls,and Elemental Sulfur" Chem.Lett.1997. 513-514 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] C.Takayama, M.Kajitani et al.: "Structural Changes Induced by Electron-Transfer Reactions. Isomerization of Alkylidene Moiety by the Reversible Metal-Carbon Bond Cleavage in the Alkylidene-Bridged Cobaltadithiolene Complex" Organometallics. 16. 3498-3503 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] A.Sugimori, M.Kajitani et al.: "Ionic and Radical Substitution in Cobaltadithiolene Ring by Dibenzoyl Peroxide" Chem.Lett.1997. 807-808 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] M.Kajitani, T.Yagisawa et al.: "Crystal Structure of [Bis(1,2-diphenylphosphino)ethane] (maleonitriledithiolato) nickel (II) [Ni(dppe)(mnt)]CH_2Cl_2" Anal.Sciences. 13. 873-874 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] C.Takayama, M.Kajitani et al.: "Reactions of Tetracyanoethylene Oxide (TCNEO) with Cobaltadithiolene Complexes" Chem.Lett.1998. 241-242 (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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