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

山墙卟啉双核过渡金属配合物的新型还原催化

• 批准号: 03640524
• 负责人: SAKAKI Shigeyoshi
• 金额: $ 0.83万
• 依托单位: Kumamoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03640524/
• 关键词: Metalloporphyrin complex; Reduction catalysis; Hydrogenation catalysis; complex Iron gable porphyrin; cyclopropanation Catalytic; Iron porphyrin complex; 屋根型架橋ポルフィリン2核錯体; ニトロベンゼン還元触媒反応; α,β不飽和エステル却元触媒反応; 亜硝酸還元酵素モデル反応

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.

以(TPP) FeCl和山墙Fe_2Cl_2还原硝基苯作为亚硝酸还原酶还原NO_2^-的模型反应。该反应不是通过偶氮苯和亚肼基苯而是通过亚硝基苯和苯基羟胺进行。观察到显着的溶剂效应；反应在THF中进行得很少，在二甘醇二甲醚中进行得适度，但在二甘醇二甲醚-MeOH中进行得相当快。 gable Fe_2Cl_2在二甘醇二甲醚-MeOH(1:1)中的催化活性约为(TPP) FeCl的两倍，这表明gable Fe_2Cl_2中的两个活性位点协同加速了这种催化还原。 UV-Vis 和 ESR 光谱表明活性物质是 Fe(II) 卟啉。这些铁卟啉也有效地催化了α，β-不饱和酯的氢化和苯乙烯的环丙烷化，分别产生饱和酯和苯基环丙烷。然而，在这些反应中，山墙形Fe_2Cl_2表现出与(TPP)FeCl几乎相同的催化活性。

项目成果

Shigeyoshi Sakaki,Shinji Mitarai,Katsutoshi Ohkubo: "New Reduction Catalysis of Metalloporphyrins.Catalyric Reduction of Nitrobenzene to Anitine with Tetraphenyl-porphyrinato-iron(3)Chloride-NaBH_4 System" Chemistry Letters. No.2. 195-198 (1991)

Shigeyoshi Sakaki，Shinji Mitarai，Katsutoshi Ohkubo：“金属卟啉的新还原催化。四苯基卟啉铁（3）氯化物-NaBH_4体系催化硝基苯还原为苯胺”化学快报。

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)

Shigeyoshi Sakaki、Shinji Mitarai、Katsutoshi Ohkubo：“金属卟啉的新型还原催化。用四苯基卟啉铁(III)氯化物-NaBH_4体系将硝基苯催化还原为苯胺。”

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. 2753-27

Toru Arai、Hiroshi Kondo、Shigeyoshi Sakaki：“[NiL](L=6,8,15,17Tetramethyldiben20[b,i][1,4,8,11]tefraaza-的二价阴离子 F_<430> 类催化作用

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-, (1991)

Shigeyoshi Sakaki 等（撰稿人）：《季刊化学评论第 13 期无机量子化学（日本化学会编）》学会出版中心，（1991 年）

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)

Shigeyoshi Sakaki 等（撰稿人）：《季刊化学评论第 13 期无机量子化学（日本化学会编）》学会出版中心，（1991 年）