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Photochemical Reactions of Organometallic Compounds

Research Project

Project/Area Number 02453016
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 構造化学
Research InstitutionMi'e University

Principal Investigator

SATO Hiroyasu  Mi'e University, Faculty of Engineering, Professor, 工学部, 教授 (20029440)

Co-Investigator(Kenkyū-buntansha) KOBAYASHI Makoto  Mi'e University, Faculty of Engineering, Research Associate, 工学部, 助手 (10215361)
Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥8,400,000 (Direct Cost: ¥8,400,000)
Fiscal Year 1991: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1990: ¥7,000,000 (Direct Cost: ¥7,000,000)
KeywordsMetalion / Molecular beam / Cluster / Laser ablation / Ion-molecule reaction / Metal complex ion / Clustered complex ion / Fragment complex ion / アンモニアクラスタ- / 気相配位化学 / 脱水素反応 / トリメチルガリウム / トリメチルアルミニウム / 多光子イオン化 / TOF質量分析 / 金属・クラスタ-錯イオン / 半導体クラスタ-
Research Abstract

In the laser ablation-molecular beam method developed by us, pulsed laser beam is focused on the surface of a metal substrate in vacuum. Laser ablation is utilized for the preparation of chemically reactive species, metal ions in this case. A molecular beam of organic or inorganic molecules, viz., benzene, ammonia or methanol, seeded in rare gas, is injected nearby. Ion-molecule reaction yields a variety of clustered complex ions such as M(C_6H_6)_n^+, M(CH_<>OH)_n^+, and M(NH_3)_n^+. For some metals, elimination of small neutrals like hydrogen or small hydrocarbon molecules is observed to give M(C_6H_6)(C_XH_Y) X*6, Y*4 and M(NH)_m(NH_3)_n, m=1, 2. Such a method, albeit very simple, is a versatile diagnosis for the study of reactions of metal ions with organic and inorganic molecules, especially with molecular clusters.
Taking the reactions of benzene clusters with metal ions as. an. example, a molecular beam of benzene in Ar(typ. C_6H_6 60 Torr/Ar 200 Torr)was used ; (C_6H_6)_n up to n=5 was found when probed by electron impact. With laser ablation of a metal substrate, reactions with M_+ ions gave clustered complex ions of the type M(C_6H_6)_n^+ (n=2-4)for most of metal ions used. Elimination of hydrogen occurred for Y^+, viz. the formation of Y(C_6H_4)^+. For Nb^+ and Ta^+, elimination of hydrogen or small hydrocarbon occurred to give fragment complex ions as Nb(C_<12>H_<10>)^+, Nb(C_<12>H_8)^+, Nb(C_<10>H_8)^+, Nb(C_<10>H_6)^+, Nb(C_8H_8)^+ and Nb(C_8H_6)_+.
In order to study reaction mechanisms in laser photo-CVD of organometallic compounds, photodissociation reactions of trimethylaluminum and trimethylgallium have been investigated both in the gas phase and on a solid substrate. Reaction intermediates such as Al, Al(CH_3)_n, Ga and Ga(CH_3)_n (n=1-2)have been probed either by laser-induced fluorescence or by multiphoton ionization followed by time-of-flight mass spectrometry.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (32 results)

All Other

All Publications (32 results)

  • [Publications] 佐藤 博保: "レ-ザ-アブレ-ションによる新規有機金属の合成" レ-ザ-研究. 18. 32-40 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H.Higashide: "Reactions of Benzene Clusters with Metal Ions as Studied by the laser Ablation-Molecular Beam Method:Observation of Clustered Complex Ions M(C_6H_6)_n^+(n>2) and Fragment Complex Ions M(C_3H_6)(C_XH_Y^+ with X<6 and Y<4" Chem.Phys.Lett.171. 297-302 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Kasatani: "Chemiluminescent Reactions Studied by Laser Ablation.Detection of AlO(B^2Σ^+) in the Al+O_2 system" Chem.Phys.Lett.174. 71-74 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T.Oka: "Reactions of Metal Ions (M^+) with Chromium Hexacarbonyl as Studied by Laser Ablation-Molecular Beam Method. Distinct Difference between the First and Second Second Series of Transition Metals Revealed in the Distribution of Product Ions 〔MCr(CO)_n〕^+ (n=0-6)" Chem.Lett.917-920 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T.Kaya: "Reactions of Ammonia Clusters with Metal Ions as Studied by the Laser Ablation-Molecular Beam Method: Observation of Clustered Complex Ions M^+(NH_3)_n(n<20) and Fragment Complex Ions with Multiple Hydrogen Elimination M^+(NH)_m(NH_3)_n (m=1,2)" Chem.Phys.Lett.186. 431-435 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Mori: "Photodissociation of Zinc Diiodide in the Gas Phase" J.Photochem.Photobiol.,A Chem.(1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H.Sato: "Photodissociation of Simple Molecules in the Gas Phase" Bunshin Publishing,Co.,Tokyo, 170 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H.Sato: "Photodissociation Reactions Mediated by Solid Surfaces,in J.F.Rabek,ed."Progress in Photochemistry and Photophysics".Vol.VI" CRC Press,Boca Raton,U.S.A., 50 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Sato: "Preparation of Novel Organometallics by Laser Ablation" Rev. Laser Engineering. 18, No. 4. 32-40 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Higashide, T. Kaya, M. Kobayashi, H. Shinohara and H. Sato: "Reactions of Benzene Clusters with Metal Ions as Studied by the Laser Ablation-Molecular Beam Method : Observation of Clustered Complex Ions M(C_6H_6)_n^+ (n>2) and Fragment Complex Ions M(C_6H_6)(C_XH_Y)^+ with X<6 and Y<4" Chem. Phys. Lett.171, No. 4. 297-302 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Kasatani, H. Higashide, H. Shinohara and H. Sato: "Chemiluminescent Reactions Studied by Laser Ablation. Detection of AlO(B^2SIGUMA^+) in the Al+O_2 system" Chem. Phys. Lett.174, No. 1. 71-74 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T. Oka, K. Kasatani, H. Shinohara and H. Sato: "Reactions of Metal Ions (M^+) with Chromium Hexacarbonyl as Studied by Laser Ablation-Molecular Beam Method. Distinct Difference between the First and Second Series of Transition Metals Revealed in the Distribution of Product Ions [MCr(CO)_n]^+ (n=0-6)" Chem. Lett.917-920 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T. Kaya, M. Kobayashi, H. Shinohara and H. Sato: "Reactions of Ammonia Clusters with Metal Ions as Studied by the Laser Ablation-Molecular Beam Method : Observation of Clustered Complex Ions M^+(NH_3)_n (n<20) and Fragment Complex Ions with Multiple Hydrogen Elimination M^+(NH)_m(NH_3)_n (m=1, 2)" Chem. Phys. Lett.186, No. 4, 5. 431-435 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Mori, K. Kasatani, M. Kawasaki, E. Ishitani, M. Kobayashi, H. Shinohara and H. Sato: "Photodissociation of Zinc Diiodide in the Gas Phase" J. Photochem. Photobiol., A Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Sato: "Photodissociation of Simple Molecules in the Gas Phase" Bunshin Publishing, Co.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Sato: "Photodissociation Reactions Mediated by Solid surfaces" Progress in Photochemistry and Photophysics. VI.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T.Oka: "Reactions of Metal Ions(M^+)with Chromium Hexacarbonyl as Studied by Laser AblationーMolecular Beam Method.Distinct Difference between the First and Second Series of Transition Metals Revealed in The Distribution of Product Ions〔MCr(CO_n〕^+(n=0ー6)" Chem.Lett. 917-920 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] H.Sato: "Organometallic Chemistry Related to AppIications for Microelectronics in Japan" Appl.Organometal.chem.5. 207-219 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] T.Kaya: "Reactions of Ammonia Clusters with Metal Ions as Studied by the Laser AblationーMolecular Beam Method:Observation of Clustered Complex Ions M^+(NH_3)_n(n<20)and Fragment Complex Ions with Multiple Hydrogen Elimination M^+(NH)_m(NH_3)_n(m=1,2)" Chem.Phys.Lett.186. 431-435 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] H.Sato: "Photodissociation of Simple Molecules in the Gas Phase,Supplement V" Res.Rep.Fac.Eng.Mie Univ.16. 89-102 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] K.Mori: "Photodissociation of Zinc Diiodide in the Gas Phase" J.Photochem.Photobiol.,A Chem.(1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] M.Kobayashi: "Photodissociation of Trimethylaluminum and Trimethylgallium on Solid Substrates" Japanese Journal of Applied Physics. 31. (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] H.Sato: "Photodissociation of Simple Molecules in the Gas Phase" Bunshin Publishing,Co.,Tokyo, 170 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] H.Sato: "Photodissociation Reactions Mediated by Solid Surfaces,in J.F.Rabek,ed.,“Progress in Photochemistry and Photophysics",Vol.VI" CRC Press,Boca Raton,U.S.A., 50 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] 佐藤 博保: "レ-ザ-アブレ-ション・分子ビ-ム法による金属イオンとアミンとの気相反応" 日本化学会誌. 1240-1245 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] H.Higashide: "Reactions of Metal Ions and Benzene as Studied by the Laser AblationーMolecular Beam Method.Pressure and Kinetic Energy Dependences of IonーMolecule Reactions" Chemical Physics Letters. 163. 485-489 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Kasatani: "LaserーInduced Deposition of Copper and Cupric Oxide Films from Cupric Acetate in Ethanol and Aqueous Solutions" Denki Kagaku. 57. 1204-1206 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] H.Sato: "Laser Photochemistry of Organometallic Compounds Related to Applications in Microelectronics" Applied Organometallic Chemistry. 3. 363-382 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] 佐藤 博保: "レ-ザ-アブレ-ションによる新規有機金属の合成" レ-ザ-研究. 18. 32-40 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] H.Higashide: "Reactions of Benzene Clusters with Metal Ions as Studied by the Laser AblationーMolecular Beam Method:observation of Clustered Complex Ions M(C_6H_6)_n^+ (n>2)" Chemical Physics Letters. 171. 297-302 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Kasatani: "Chemiluminescent Reactions Studied by Laser Ablation.Detection of AlO(B^2Σ^+) in the Al + O_2 System" Chemical Physics Letters. 174. 71-74 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Mori: "Photodissociation of Zinc Diiodide in the Gas Phase" J.Photochem.Photobiol.A Chemistry.

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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