TY - JOUR
T1 - C-H activation on platinum, a mechanistic study
AU - Lebrilla, Carlito B.
AU - Maier, Wilhelm F.
PY - 1986
Y1 - 1986
N2 - C-H activation on heterogeneous Pt catalysts is found to be most facile at low Pt dispersion and surface structure insensitive at dispersions above 10%. Two distinct processes have been identified which lead to the formation of mono- and polydeuterated products, respectively. The ratio of mono-/polydeuteration processes increases with increasing disper ion. Evidence is provided for the formation of π-intermediates as the initiator of polydeuteration. The most facile mechanism of exchange propagation in a single molecule is through a π-allyl-type interconversion. The deuterium in monodeuterated n-hexane is located at the terminal position by high-resolution deuterium NMR. NMR spectroscopy also provides evidence for steric effects which prevent significant H/D exchange at positions close to quaternary centers. C-H activation appears to be sensitive to steric hindrance, the C-H bond energy, and the partial pressure of the substrate.
AB - C-H activation on heterogeneous Pt catalysts is found to be most facile at low Pt dispersion and surface structure insensitive at dispersions above 10%. Two distinct processes have been identified which lead to the formation of mono- and polydeuterated products, respectively. The ratio of mono-/polydeuteration processes increases with increasing disper ion. Evidence is provided for the formation of π-intermediates as the initiator of polydeuteration. The most facile mechanism of exchange propagation in a single molecule is through a π-allyl-type interconversion. The deuterium in monodeuterated n-hexane is located at the terminal position by high-resolution deuterium NMR. NMR spectroscopy also provides evidence for steric effects which prevent significant H/D exchange at positions close to quaternary centers. C-H activation appears to be sensitive to steric hindrance, the C-H bond energy, and the partial pressure of the substrate.
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M3 - Article
AN - SCOPUS:21844445702
VL - 108
SP - 1606
EP - 1616
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 7
ER -