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- Title
Propane σ-Complexes on PdO(101): Spectroscopic Evidence of the Selective Coordination and Activation of Primary C-H Bonds.
- Authors
Zhang, Feng; Pan, Li; Choi, Juhee; Mehar, Vikram; Diulus, John T.; Asthagiri, Aravind; Weaver, Jason F.
- Abstract
Achieving selective C-Hbond cleavage is critical for developing catalytic processes that transform small alkanes to value-added products. The present study clarifies the molecular- level origin for an exceptionally strong preference for propane to dissociate on the crystalline PdO(101) surface via primary C-H bond cleavage. Using reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations, we show that adsorbed propane scomplexes preferentially adopt geometries on PdO(101) in which only primary C-H bonds datively interact with the surface Pd atoms at low propane coverages and are thus activated under typical catalytic reaction conditions. We show that a propane molecule achieves maximum stability on PdO(101) by adopting a bidentate geometry in which a H- Pd dative bond forms at each CH3 group. These results demonstrate that structural registry between the molecule and surface can strongly influence the selectivity of a metal oxide surface in activating alkane C-H bonds.
- Subjects
PROPANE; CARBON-hydrogen bonds; SCISSION (Chemistry); COORDINATE covalent bond; DENSITY functional theory
- Publication
Angewandte Chemie, 2015, Vol 127, Issue 47, p14113
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201505237