title: Photocatalytic acceptorless alkane dehydrogenation: scope, mechanism, and conquering deactivation with carbon dioxide.
abstract: Alkane dehydrogenation is of special interest for basic science but also offers interesting opportunities for industry. The existing dehydrogenation methodologies make use of heterogeneous catalysts, which suffer from harsh reaction conditions and a lack of selectivity, whereas homogeneous methodologies rely mostly on unsolicited waste generation from hydrogen acceptors. Conversely, acceptorless photochemical alkane dehydrogenation in the presence of trans-Rh(PMe3 )2 (CO)Cl can be regarded as a more benign and atom efficient alternative. However, this methodology suffers from catalyst deactivation over time. Herein, we provide a detailed investigation of the trans-Rh(PMe3 )2 (CO)Cl-photocatalyzed alkane dehydrogenation using spectroscopic and theoretical investigations. These studies inspired us to utilize CO2 to prevent catalyst deactivation, which leads eventually to improved catalyst turnover numbers in the dehydrogenation of alkanes that include liquid organic hydrogen carriers.
authors.affiliation: Leibniz-Institut für Katalyse an der Universität Rostock, Albert-Einstein-Straße 29a, 18059 Rostock (Germany).
authors.forename: Abhishek Dutta
authors.initials: AD
authors.lastname: Chowdhury
authors.forename: Jennifer
authors.initials: J
authors.lastname: Julis
authors.forename: Kathleen
authors.initials: K
authors.lastname: Grabow
authors.forename: Bernd
authors.initials: B
authors.lastname: Hannebauer
authors.forename: Ursula
authors.initials: U
authors.lastname: Bentrup
authors.forename: Martin
authors.initials: M
authors.lastname: Adam
authors.forename: Robert
authors.initials: R
authors.lastname: Franke
authors.forename: Ralf
authors.initials: R
authors.lastname: Jackstell
authors.forename: Matthias
authors.initials: M
authors.lastname: Beller
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D006865:Hydrogenation; D008958:Models, Molecular; D008968:Molecular Conformation; D055668:Photochemical Processes
chemical_list: D000473:Alkanes; D002245:Carbon Dioxide
keywords: alkanes; dehydrogenation; homogeneous catalysis; photochemistry; rhodium