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Propane σ‐Complexes on PdO(101): Spectroscopic Evidence of the Selective Coordination and Activation of Primary CH Bonds
Author(s) -
Zhang Feng,
Pan Li,
Choi Juhee,
Mehar Vikram,
Diulus John T.,
Asthagiri Aravind,
Weaver Jason F.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201505237
Subject(s) - propane , chemistry , density functional theory , alkane , catalysis , molecule , adsorption , denticity , infrared spectroscopy , photochemistry , bond cleavage , crystallography , computational chemistry , organic chemistry , crystal structure
Achieving selective CH bond 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 CH bond cleavage. Using reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations, we show that adsorbed propane σ‐complexes preferentially adopt geometries on PdO(101) in which only primary CH 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 HPd dative bond forms at each CH 3 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 CH bonds.