Dinuclear ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects

Ru-aqua complex {[RuII(trpy)(H2O)] 2(μ-pyr-dc)}+ is a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes. High turnover numbers (TNs), up to 17000, and turnover frequencies (TOF), up to 24120 h-1 (6.7 s -1), have been obtained using PhIO as oxidant. This species presents an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides. In addition, it shows different reactivity to cis and trans olefins due to a substrate orientation supramolecular effect transmitted by its ligand scaffold. This effect together with the impressive reaction rates are rationalized using electrochemical techniques and DFT calculations. A new Ru-aqua complex that behaves as a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes is reported. High turnover numbers and frequencies are obtained by using PhIO as oxidant. The complex shows an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides (see figure). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Citation

Di Giovanni, C., Poater, A., Benet-Buchholz, J., Cavallo, L., Solà, M., & Llobet, A. (2014). Dinuclear Ru-Aqua Complexes for Selective Epoxidation Catalysis Based on Supramolecular Substrate Orientation Effects. Chemistry - A European Journal, 20(14), 3898–3902. doi:10.1002/chem.201304699

Acknowledgements

This research was supported financially by MINECO (CTQ2011-23156/BQU, CTQ2010-21497 and PRI-PIBIN-2011-1278), ICIQ, FEDER fund (UNGI08-4E-003), ICREA Academia, Generalitat de Catalunya (2009SGR637); Ramon y Cajal contract (RYC-2009-05226) of MINECO, and Career Integration Grant (CIG09-GA-2011-293900) of the European Commission. COST Actions CM1205 and CM1202 are also gratefully acknowledged.

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[Dataset]
Di Giovanni, C., Poater, A., Benet-Buchholz, J., Cavallo, L., Sola, M., & Llobet, A. (2015). CCDC 1429305: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jz9mf. DOI: 10.5517/cc1jz9mf HANDLE: 10754/624475

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http://hdl.handle.net/10754/563429

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