Tuning Cyclohexane Oxidation: Combination of Microwave Irradiation and Ionic Liquid with the C-Scorpionate [FeCl2(Tpm)] Catalyst

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• 作者：Ana P. C. Ribeiro ; Luísa M. D. R. S. Martins ; Maxim L. Kuznetsov ; Armando J. L. Pombeiro
• 刊名：Organometallics
• 出版年：2017
• 出版时间：January 9, 2017
• 年：2017
• 卷：36
• 期：1
• 页码：192-198
• 全文大小：377K
• ISSN：1520-6041

文摘

For the first time, microwave (MW) irradiation was successfully applied to peroxidative cyclohexane oxidation catalyzed by a C-scorpionate complex, [FeCl₂(Tpm)] (1; Tpm = hydrotris(pyrazol-1-yl)methane), providing a highly selective and fast eco-friendly procedure to produce a KA (cyclohexanol + cyclohexanone) oil mixture (up to ca. 100% selectivity) with 28% yield in 1 h at 50 °C in MeCN. Water, organics, and ionic liquids (ILs, [bmim][N(CN)₂] and [bmim][BF₄]) were used as solvents, and their interactions with 1 were determined by DFT calculations. The possibility to recycle and reuse 1 (up to nine consecutive cycles) without loss of activity is also observed for the IL [bmim][BF₄]. Moreover, higher catalytic activities under additive-free conditions are obtained with the ILs in comparison to those with the other solvents. Tuning the alcohol/ketone selectivity is also possible by choosing the appropriate IL solvent.