Towards a Practical Development of Light‐Driven Acceptorless Alkane Dehydrogenation. Issue 25 (14th May 2014)

• Record Type: Journal Article
• Authors: Chowdhury, Abhishek Dutta; Weding, Nico; Julis, Jennifer; Franke, Robert; Jackstell, Ralf; Beller, Matthias
• Is Part Of: Angewandte Chemie international edition. Volume 53:Issue 25(2014)
• Page Start: 6477
• Page End: 6481
• Publication Date: 2014-05-14
• Subjects: dehydrogenation -- olefination -- photochemistry -- rhodium -- homogeneous catalysis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201402287
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The efficient catalytic dehydrogenation of alkanes to olefins is one of the most investigated reactions in organic synthesis. In the coming years, an increased supply of shorter‐chain alkanes from natural and shale gas will offer new opportunities for inexpensive carbon feedstock through such dehydrogenation processes. Existing methods for alkane dehydrogenation using heterogeneous catalysts require harsh reaction conditions and have a lack of selectivity, whereas homogeneous catalysis methods result in significant waste generation. A strong need exists for atom‐efficient alkane dehydrogenations on a useful scale. Herein, we have developed improved acceptorless catalytic systems under optimal light transmittance conditions using trans ‐[Rh(PMe3 )2 (CO)Cl] as the catalyst with different additives. Unprecedented catalyst turnover numbers are obtained for the dehydrogenation of cyclic and linear (from C4 ) alkanes and liquid organic hydrogen carriers. These reactions proceed with unique conversion, thereby providing a basis for practical alkane dehydrogenations. Abstract : Blue (light) is green : The efficient light‐induced atom‐economical alkane dehydrogenation of various linear and cyclic alkanes (including shale gas constituents and liquid organic hydrogen carriers) was accomplished using trans ‐[Rh(PMe3 )2 (CO)Cl] as a catalyst in the presence of a specific nitrogenous additive. It provides a benign alternative to the direct use of alkanes as olefin feedstocks.