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; 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.

通过（TPP）FECL和Gable Fe_2Cl_2作为NO_2^ - 通过亚硝酸盐还原酶减少的模型反应进行硝基苯的还原。该反应不是通过偶氮苯和氢苯苯进行的，而是硝基苯和苯基羟胺。观察到明显的溶剂作用；反应在THF中很少进行，在Diglyme中适度进行，但在Diglyme-Meoh中进行了相当大的发展。山墙FE_2CL_2的催化活性约为Diglyme-Meoh（1：1）的两次（TPP）FECL，这表明在Gable FE_2CL_2中的两个有效引用可以使这种催化降低加速。 UV-VIS和ESR光谱表明活性物种是Fe（II）卟啉。这些Fe-porphyrins也有效地催化了α，β-不饱和酯和苯乙烯的氢化，分别得出饱和的酯和苯基环丙烷。但是，在这些反应中，山墙FE_2CL_2表现出与（TPP）FECL几乎相同的催化活性。