Surprising Differences of Alkane C‐H Activation Catalyzed by Ruthenium Nanoparticles: Complex Surface‐Substrate Recognition?. Issue 19 (17th August 2018)

• Record Type: Journal Article
• Authors: Rothermel, Niels; Bouzouita, Donia; Röther, Tobias; de Rosal, Iker; Tricard, Simon; Poteau, Romuald; Gutmann, Torsten; Chaudret, Bruno; Limbach, Hans‐Heinrich; Buntkowsky, Gerd
• Is Part Of: ChemCatChem. Volume 10:Issue 19(2018)
• Page Start: 4243
• Page End: 4247
• Publication Date: 2018-08-17
• Subjects: Alkane C−H activation -- Catalysis -- Density functional calculations -- Deuterium isotopic labeling -- Nanoparticles; Catalysis -- Periodicals; 541.39505
• DOI: 10.1002/cctc.201801022
• Languages: English
• ISSNs: 1867-3880

Abstract

Abstract: The activation of C−H bonds of alkanes remains a major challenge for chemistry. In a series of deuteration experiments with D2 in contact with bis‐(diphenylphosphino) butane (dppb) stabilized ruthenium nanoparticles (liquid substrates, 60 °C, 6 bar D2 ) we have observed a surprisingly large reactivity of cyclopentane as compared to cyclohexane and other alkanes. DFT calculations using a ligand‐free Ru13 H17 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. Abstract : Lazy chair : Bis‐(diphenylphosphino) butane stabilized ruthenium nanoparticles catalyze C−H activation and deuteration of alkanes with D2 gas. Surprisingly, cyclopentane exhibits a substantially larger reactivity as compared to cyclohexane and other flexible alkanes. The effect is discussed in terms of a complex nanoparticle surface whose catalytic activity discriminates between different substrates according to their structure, similarly to substrate recognition by enzymes.