Computational Mechanism Investigation of C=C Bond Hydrogenation Catalyzed by Rhodium Hydride

The hydrogenation of unsaturated carbons is a commonly used synthetic tool in pharmaceutical and industrial production. Recently, the Norton group realized highly selective hydrogenation of C=C bonds catalyzed by a rhodium hydride. Despite the great efforts made by experimentalists, details regarding the mechanism remained unclear. In this work, detailed DFT calculations were carried out to elucidate the principal features of this transformation. For enones we find that two possible competing mechanisms proposed by the experimental groups are computationally excluded, our proposed alternative mechanism with a total barrier of 20.0 kcal mol^-1 is theoretically feasible, solvent methanol to also plays a crucial role in assisting β-hydrogenation in addition to being the hydrogen source for α-hydrogenation, and the cross-polarization of the substrate enone-conjugated system to result in an enhanced charge density of the α-carbon, which favors being hydrogenated first. For isolated alkenes, neither of the two possible competing mechanisms can be excluded computationally and which carbon atom is first hydrogenated depends on the electronic properties of the substrate itself. The combination of rhodium and C=C bonds changes the electronic properties of H on the rhodium hydride and enhances its hydrogenation activity.