Surprising Differences of Alkane C‐H Activation Catalyzed by Ruthenium Nanoparticles: Complex Surface‐Substrate Recognition?

Abstract

Abstract The activation of C−H bonds of alkanes remains a major challenge for chemistry. In a series of deuteration experiments with D 2 in contact with bis‐(diphenylphosphino) butane (dppb) stabilized ruthenium nanoparticles (liquid substrates, 60 °C, 6 bar D 2 ) we have observed a surprisingly large reactivity of cyclopentane as compared to cyclohexane and other alkanes. DFT calculations using a ligand‐free Ru 13 H 17 model cluster as catalyst indicate oxidative C−H cleavage of the bound substrates as rate limiting reaction step. They also indicate similar binding and activation enthalpies of reactions of cyclopentane and cyclohexane.