High Activity and Selectivity for Catalytic Alkane–Alkene Transfer (De)hydrogenation by (tBuPPP)Ir and the Importance of Choice of a Sacrificial Hydrogen Acceptor

• Published in: Organometallics 2022-11, Vol.41 (22), p.3426-3434
• Main Authors: Gordon, Benjamin M., Parihar, Ashish, Hasanayn, Faraj, Goldman, Alan S.
• Format: Article
• Language: English
• Subjects: 10 SYNTHETIC FUELS; alkanes; C-H bonds; carbon; catalysis; ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; hydrocarbons; hydrogen; hydrogenation; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; olefins; organic reactions; selectivity
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.2c00401

The triphosphorus-coordinating pincer iridium fragment (tBuPPP)Ir was recently reported to be highly active for the catalytic dehydrogenation of n-alkanes. Dehydrogenation is calculated to be highly regioselective for the terminal position of n-alkanes. The extremely high intermolecular selectivity observed in n-alkane/cycloalkane competition experiments supports the prediction of extremely high regioselectivity for dehydrogenation of n-alkanes. The use of sterically unhindered hydrogen acceptors is key to observing the high activity of the (tBuPPP)Ir fragment. 4,4-Dimethylpent-1-ene (TBP) is found to be particularly convenient for this purpose. With the commonly used hydrogen acceptor 3,3-dimethylbut-1-ene (TBE), (tBuPPP)Ir affords n-alkane dehydrogenation at a rate no different than that obtained with the well-known fragment (iPrPCP)­Ir. However, with the use of TBP as acceptor, (tBuPPP)Ir shows much greater activity for n-alkane transfer dehydrogenation than previously reported catalysts, affording appreciable rates even at 50 °C, an unprecedentedly low temperature for catalytic alkane transfer dehydrogenation. Also critical to the identification of (tBuPPP)Ir as a highly effective catalyst is the use of n-alkane substrate rather than the commonly used “model” dehydrogenation substrate, cyclooctane, with which dehydrogenation rates are much lower than those with n-alkanes.