In Situ Generation and Immobilization of an Activated Rh Complex Catalyst in a Metal–Organic Framework for Hydrogenation at Low H2 Pressure

Hydrogenation reactions under low‐pressure H 2 atmosphere are highly relevant from the safety viewpoint, because H 2 gas is highly flammable in air and explosions can be triggered by spark, heat, or sunlight. In this work, an Rh complex/MOF hybrid was synthesized and used as catalyst for the hydrogenation of alkene substrates. Thanks to the activation of the Rh complex catalyst during the immobilization process and the intrinsic gas‐condensation property of MOFs, the resulting composite showed much higher catalytic activity than the complex catalyst itself. Moreover, the composite can maintain its catalytic activity even at low H 2 pressures that cannot support the reaction with the complex catalyst alone. Furthermore, in contrast to the complex catalyst, the composite maintained its catalytic activity even without solvent, and thus provides an environmentally friendly approach to catalysis.