Hydrogen Activation and Hydrogenolysis Facilitated by Late-Transition-Metal-Aluminum Heterobimetallic Complexes
Previously reported heterobimetallic rhodium-aluminum and iridium-aluminum alkyl complexes are shown to activate hydrogen, generating the corresponding alkane. Kinetic data indicate a mechanistic difference between the iridium- and rhodium-based systems. In both cases the transition metal is an active participant in the release of alkane from the aluminum center. For iridium-aluminum species, experimental mechanistic data suggest that multiple pathways occur concomitantly with each other: one being the oxidative addition of hydrogen followed by proton transfer resulting in alkane generation. Computational data indicate a reasonable barrier to formation of an iridium dihydride intermediate observed experimentally. In the case of the rhodium-aluminum species, hydrides are not observed spectroscopically, though a reasonable barrier to formation of this thermodynamically unstable species has been calculated. Alternative mechanistic possibilities are discussed and explored computationally. Cooperative hydrogenolysis mechanisms are computed to be energetically unfeasible for both metal centers.
Charles, R., Yokley, T., Schley, N., Deyonker, N., & Brewster, T. (2019). Hydrogen Activation and Hydrogenolysis Facilitated by Late-Transition-Metal-Aluminum Heterobimetallic Complexes. Inorganic Chemistry, 58 (19), 12635-12645. https://doi.org/10.1021/acs.inorgchem.9b01359