Robert Crabtree is renowned for his influential work on hydrogenation, particularly his contributions to the development of the Crabtree catalyst. This catalyst, utilizing iridium as the active metal, displays exceptional efficiency, regio- and stereoselectivity in hydrogenation reactions. Notably, when terpinen-4-ol undergoes hydrogenation, the Crabtree catalyst exhibits a remarkable preference of 1000:1 for adding hydrogen to the substrate face containing the OH group. In contrast, the hydrogenation reaction with Palladium on carbon only achieves a selectivity ratio of 20:80. The chelation of the alcohol to the catalyst is evident from the identification of a catalyst-substrate complex involving norbornene-2-ol.
During his early research, Crabtree also focused on C–H bond activation. Crabtree's groundbreaking contribution in this area was reversing the hydrogenation reactions he developed before, particularly in stoichiometric alkane dehydrogenation. He utilized tert-butylethylene as a hydrogen acceptor to facilitate the release of hydrogen during the dehydrogenation of cyclooctane, forming bound cyclooctadiene. This discovery demonstrated one of the earliest instances of intermolecular C–H activation using a homogeneous metal complex. This achievement played a significant role in his tenure award and academic success