Dinuclear Ru–Aqua Complexes for Selective Epoxidation Catalysis Based on Supramolecular Substrate Orientation Effects |
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| Authors: | Dr. Carlo Di Giovanni Dr. Albert Poater Dr. Jordi Benet‐Buchholz Prof. Luigi Cavallo Prof. Miquel Solà Prof. Antoni Llobet |
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| Affiliation: | 1. Institute of Chemical Research of Catalonia (ICIQ), Av. Pa?sos Catalans 16, 43007 Tarragona (Spain), Departament de Química, Universitat Autònoma de Barcelona Cerdanyola del Vallès, 08193, Barcelona (Spain);2. Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona (Spain);3. KAUST Catalysis Center, 4700 King Abdullah University of Science and Technology, Thuwal 23955‐6900 (Kingdom of Saudi Arabia) |
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| Abstract: | 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. |
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| Keywords: | density functional calculations electrochemistry epoxidation ruthenium supramolecular redox catalysis |
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