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Title: Proton transfer from alkane radical cations to alkane molecules: Selectivity with respect to the site of proton donation and proton acceptance
Authors: Ceulemans, Jan # ×
Issue Date: Jan-2002
Publisher: Amer chemical soc
Series Title: Accounts of Chemical Research vol:35 issue:7 pages:523-531
Abstract: Information on the donor and acceptor site selectivity in the proton transfer from n-alkane radical cations to n-alkane molecules is gathered from gamma-irradiated frozen CCl3F/n-alkane solutions (symmetric transfer) and mixed n-alkane crystals (asymmetric transfer) by EPR spectroscopy at 77 K and gas chromatographic analysis after melting. The proton-donor site is related very strictly to the structure of the semi-occupied molecular orbital of the parent radical cation, with proton transfer taking place from those C-H bonds that carry appreciable unpaired-electron and positive-charge density. Proton acceptance is restricted to C-H bonds at secondary carbon atoms (no proton transfer to C-C bonds nor to C-H bonds at primary carbon atoms), with a preference for the penultimate position and equal (but considerably lower) transfer to the interior sites. In mixed n-alkane crystals, additional selectivity with respect to the site of proton acceptance results from structural factors in combination with the donor site selectivity (structurally determined acceptor site selectivity).
URI: 
ISSN: 0001-4842
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
× corresponding author
# (joint) last author

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