New Reduction Catalysis by Dinuclear Transition-metal Complexes of Gable Porphyrin

1992 Fiscal Year Final Research Report Summary

• Project/Area Number: 03640524
• Research Category: Grant-in-Aid for General Scientific Research (C)
• Allocation Type: Single-year Grants
• Research Field: 無機・錯塩・放射化学
• Research Institution: Kumamoto University
• Principal Investigator: SAKAKI Shigeyoshi Kumamoto University, Faculty of Engineering Professor, 工学部, 教授 (20094013)
• Co-Investigator(Kenkyū-buntansha): ARAI Toru Kumamoto University, Faculty of Engineering Research Associate, 工学部, 助手 (50222716)
• Project Period (FY): 1991 – 1992
• Keywords: Metalloporphyrin complex / Reduction catalysis / Hydrogenation catalysis / complex Iron gable porphyrin / cyclopropanation Catalytic / Iron porphyrin complex

Research Abstract

Reduction of nitrobenzene was performed by (TPP) FeCl and gable Fe_2Cl_2 as a model reaction of NO_2^- reduction by nitrite reductase. This reaction proceeds via not azobenzene and hydrazobenzene but nitrosobenzene and phenylhydroxylamine. Significant solvent effects were observed; reaction proceeds little in THF, moderately in diglyme, but considerably in diglyme-MeOH. The catalytic activity of gable Fe_2Cl_2 is about twice of (TPP) FeCl in diglyme-MeOH(1:1), suggesting that the two active cites in gable Fe_2Cl_2 cooperatively accelerates this catalytic reduction. UV-Vis and ESR spectra suggest that active species is Fe(II) porphyrin. Hydrogenation of alpha,beta-unsaturated esters and cyclopropanation of stylene were also efficiently catalyzed by these Fe-porphyrins, yielding the saturated ester and phenylcyclopropane respectively. In these reactions, however, gable Fe_2Cl_2 exhibits almost the same catalytic activity as (TPP)FeCl.

Research Products

• [Publications] Shigeyoshi Sakaki,Shinji Mitarai,Katsutoshi Ohkubo: "New Reduction Catalysis of Metalloporphyrins.Catalytic Reduction of Nitrobenzene to Aniline with Tetraphenyl-porphyrinato-iron(III)Choride-NaBH_4 System." Chemistry Letters. No.2. 195-198 (1991)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shigeyoshi Sakaki,Takahito Sagara,Toru Arai,Tasuya Kojima,Tomohiko Ogata,Katsutoshi Ohkubo: "Metalloporphyrin-catalyzed hydrogenation of α,β-unsaturated Esters" Journal of Molecular Catalysis. 75. L33-L37 (1992)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Toru Arai,Hiroshi Kondo,Shigeyoshi Sakaki: "Factor F_<430>-like Catalysis of [NiL](L=Dianion of 6,8,15,17Tetramethyldiben20[b,i][1,4,8,11]tefraaza-cyclotetradecine)in the Reduction of Alkyl Halides" Journal of Chemical Society,Dalton Transactions. 2753-2754 (1992)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 榊 茂好他(分担執筆): "季刊化学総説No.13無機量子化学(日本化学会編)" 学会出版センター, (1991)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shigeyoshi Sakaki, Shinji Mitarai, Katsutoshi Ohkubo: "New Reduction Catalysis of Metalloporphyrins. Catalytic Reduction of Nitrobenzene to Aniline with Tetraphenyl-porphyrinato-iron(III) Chloride-NaBH_4 System." Chemistry Letters. No.2. 195-198 (1991)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Shigeyoshi Sakaki, Takahito Sagara, Toru Arai, tatsuya Kojima, Tomohiko Ogata, Katsutoshi Ohkubo: "Metalloporphyrin-catalyzed hydrogenation of alpha,beta-Unsaturated Esters." Journal of Molecular Catalysis. Vol.75. L33-L37 (1992)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Toru Arai, Hiroshi Kondo, Shigeyoshi Sakaki: "Factor F_<430>-like Catalysis of [NiL] (L = Dianion of 6,8,15,17-TETRAMETHYLDIBENZO[B,I][1,4,8,11]-Tetraazacyclotetradecine) in the Reduction of Alkyl Halides." Journal of Chemical Society, Dalton Transactions. 2753-2754 (1992)
  • Description: 「研究成果報告書概要(欧文)」より