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gable Fe_2Cl_2还原硝基苯作为亚硝酸盐还原酶还原NO_2 ~-的模型反应。该反应不是通过偶氮苯和氢化偶氮苯进行的，而是通过亚硝基苯和苯基羟胺进行的。观察到显著的溶剂效应;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中进行得相当多。在二甘醇二甲醚-甲醇（1：1）体系中，gable Fe_2Cl_2的催化活性约为（TPP）FeCl的2倍，表明gable Fe_2Cl_2中的两个活性中心协同促进了该催化还原反应。UV-Vis和ESR谱表明活性物种为Fe（II）卟啉。这些铁卟啉还可以有效地催化α，β-不饱和酯的氢化反应和苯乙烯的环丙烷化反应，分别得到饱和酯和苯基环丙烷。在这些反应中，gable 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）

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)

Shigeyoshi Sakaki、Takahito Sagara、Toru Arai、tatsuya Kojima、Tomohiko Ogata、Katsutoshi Ohkubo：“金属卟啉催化 α,β-不饱和酯的氢化。”