Mechanism of deuterium addition and exchange of propene over Pd/SiO2 at lower temperatures: Direct evidence for intramolecular double bond migration during hydrogenation

S NAITO

doi:10.1016/0021-9517(86)90174-0

Mechanism of deuterium addition and exchange of propene over Pd/SiO2 at lower temperatures: Direct evidence for intramolecular double bond migration during hydrogenation

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S NAITO

書誌事項

公開日: 1986-12

権利情報

https://www.elsevier.com/tdm/userlicense/1.0/

DOI

10.1016/0021-9517(86)90174-0

公開者: Elsevier BV

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説明

The mechanism of the deuterium addition and exchange reaction of propene over PdSiO2 at lower temperatures was elucidated by applying microwave spectroscopy as well as kinetic study. The activation energies for the exchange of each hydrogen in propene and for the deuterium addition were determined. In the absence of deuterium molecule, the hydrogen exchange reaction proceeds via dissociative mechanism including n-propenyl, sec-propenyl, and allylic adsorbed species. In the presence of gaseous deuterium molecules, however, both addition and exchange processes proceed via associative mechanism involving n-propyl as well as sec-propyl species; the methyl groups of the latter species are not equivalent for abstraction of a hydrogen atom. In addition, direct evidence was obtained for the intramolecular double bond migration process during hydrogenation, which may proceed via an intermediate with a bridged hydrogen between C1 and C3 carbons of propene.