Oxidative decarboxylation of carboxylic acids with tetrabutylammonium periodate catalyzed by manganese(III) meso-tetraarylporphyrins:: Effect of metals, meso-substituents, and anionic axial ligands
Oxidative decarboxylation of carboxylic acids with tetrabutylammonium periodate catalyzed by manganese(III) meso-tetraarylporphyrins:: Effect of metals, meso-substituents, and anionic axial ligands
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DOI：
10.1016/s1872-2067(07)60080-1
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发表时间：
2007-11-01
影响因子：
16.5
通讯作者：
Zakavi, Saeed
中科院分区：
文献类型：
--
作者：
Karimipour, Gholam Reza;Karami, Bahador;Zakavi, Saeed
锰中四芳基卟啉与四丁基高碘酸铵（n-BU4NIO4）和咪唑（ImH）结合，为羧酸的氧化脱羧提供了有效的催化体系。中位四芳基卟啉具有吸电子和/或在中位位置有大量芳基，降低了金属卟啉的催化活性。虽然ImH的存在和金属中心的选择对金属卟啉的催化性能至关重要，但反离子在该催化体系中起着重要作用。而Mn (TPP) CN/n-BU4NIO4/ImH体系的催化活性最好。假设一个催化循环，其中二苯基乙酸的氧化脱羧涉及到高价mn -o物种与底物的相互作用。已经尝试可视化可能的相互作用和电子变化负责形成相应的羰基产物。
In association with tetrabutylammonium periodate (n-BU4NIO4) and imidazole (ImH), manganese meso-tetraarylporphyrins have provided an effective catalytic system for the oxidative decarboxylation of carboxylic acids. Meso-tetraarylporphyrins bearing electron withdrawing and/or bulky aryl groups at meso-positions lowered the catalytic activity of the metalloporphyrins. Although the presence of ImH and the choice of the metal center are crucial for the catalytic properties of the metalloporphyrins, the counter Ion plays an important role in this catalytic system. However, the best catalytic activity has been observed for the Mn (TPP) CN/n-BU4NIO4/ImH system. A catalytic cycle is postulated, in which the oxidative decarboxylation of diphenylacetic acid involves the interaction of a high-valent Mn-oxo species with the substrate. Attempts have been made to visualize the possible interactions and electronic changes responsible for the formation of the corresponding carbonyl products.