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Bioinspired Oxidation of Methane in the Confined Spaces of Molecular Cages
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-05-13 00:00:00 , DOI: 10.1021/acs.inorgchem.9b00199 Sk Asif Ikbal 1 , Cédric Colomban 2 , Dawei Zhang 3 , Magalie Delecluse 2 , Thierry Brotin 3 , Véronique Dufaud 4 , Jean-Pierre Dutasta 3 , Alexander B. Sorokin 1 , Alexandre Martinez 2
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-05-13 00:00:00 , DOI: 10.1021/acs.inorgchem.9b00199 Sk Asif Ikbal 1 , Cédric Colomban 2 , Dawei Zhang 3 , Magalie Delecluse 2 , Thierry Brotin 3 , Véronique Dufaud 4 , Jean-Pierre Dutasta 3 , Alexander B. Sorokin 1 , Alexandre Martinez 2
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Non-heme iron, vanadium, and copper complexes bearing hemicryptophane cavities were evaluated in the oxidation of methane in water by hydrogen peroxide. According to 1H nuclear magnetic resonance studies, a hydrophobic hemicryptophane cage accommodates a methane molecule in the proximity of the oxidizing site, leading to an improvement in the efficiency and selectivity for CH3OH and CH3OOH compared to those of the analogous complexes devoid of a hemicryptophane cage. While copper complexes showed low catalytic efficiency, their vanadium and iron counterparts exhibited higher turnover numbers, ≤13.2 and ≤9.2, respectively, providing target primary oxidation products (CH3OH and CH3OOH) as well as over-oxidation products (HCHO and HCOOH). In the case of caged vanadium complexes, the confinement effect was found to improve either the selectivity for CH3OH and CH3OOH (≤15%) or the catalytic efficiency. The confined space of the hydrophobic pocket of iron-based supramolecular complexes plays a significant role in the improvement of both the selectivity (≤27% for CH3OH and CH3OOH) and the turnover number of methane oxidation. These results indicate that the supramolecular approach is a promising strategy for the development of efficient and selective bioinspired catalysts for the mild oxidation of methane to methanol.
中文翻译：
分子笼密闭空间中甲烷的生物启发性氧化
在过氧化氢对水中甲烷的氧化作用中，评估了带有半色氨酸空穴的非血红素铁，钒和铜络合物。根据1 H核磁共振研究，疏水性半色氨酸笼子在氧化位点附近容纳了一个甲烷分子，与没有类似物的类似物相比，对CH 3 OH和CH 3 OOH的效率和选择性有所提高。半胱氨酸笼子。尽管铜配合物显示出较低的催化效率，但它们的钒和铁对应物显示出更高的周转率，分别≤13.2和≤9.2，提供了目标初级氧化产物（CH 3 OH和CH 3OOH）以及过氧化产物（HCHO和HCOOH）。在笼状钒配合物的情况下，发现限制作用可以提高对CH 3 OH和CH 3 OOH（≤15％）的选择性或催化效率。铁基超分子配合物的疏水口袋的密闭空间在选择性（CH 3 OH和CH 3 OOH≤27％）和甲烷氧化转换数的提高中起着重要作用。这些结果表明，超分子方法是开发有效和选择性的生物启发催化剂以将甲烷轻度氧化为甲醇的有前途的策略。
更新日期：2019-05-13
中文翻译：
分子笼密闭空间中甲烷的生物启发性氧化
在过氧化氢对水中甲烷的氧化作用中，评估了带有半色氨酸空穴的非血红素铁，钒和铜络合物。根据1 H核磁共振研究，疏水性半色氨酸笼子在氧化位点附近容纳了一个甲烷分子，与没有类似物的类似物相比，对CH 3 OH和CH 3 OOH的效率和选择性有所提高。半胱氨酸笼子。尽管铜配合物显示出较低的催化效率，但它们的钒和铁对应物显示出更高的周转率，分别≤13.2和≤9.2，提供了目标初级氧化产物（CH 3 OH和CH 3OOH）以及过氧化产物（HCHO和HCOOH）。在笼状钒配合物的情况下，发现限制作用可以提高对CH 3 OH和CH 3 OOH（≤15％）的选择性或催化效率。铁基超分子配合物的疏水口袋的密闭空间在选择性（CH 3 OH和CH 3 OOH≤27％）和甲烷氧化转换数的提高中起着重要作用。这些结果表明，超分子方法是开发有效和选择性的生物启发催化剂以将甲烷轻度氧化为甲醇的有前途的策略。
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