Open AccessOxygen transfer involving nonheme iron: the influence of leaving group ability on the rate constant for oxygen transfer to (EDTA)Fe(III) from peroxycarboxylic acids and hydroperoxides.
Author(s) -
Balasubramanian Palaniappan,
Thomas C. Bruice
Publication year - 1987
Publication title -
proceedings of the national academy of sciences of the united states of america
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.011
H-Index - 771
eISSN - 1091-6490
pISSN - 0027-8424
DOI - 10.1073/pnas.84.7.1734
Subject(s) - chemistry , alkyl , oxygen , heterolysis , reaction rate constant , moiety , medicinal chemistry , oxygen atom , solvent , inorganic chemistry , stereochemistry , organic chemistry , kinetics , molecule , catalysis , physics , quantum mechanics
Ethylenediaminetetraacetato iron(III) [(EDTA)Fe(III)] has been shown to react with a series of four peroxycarboxylic acids and four alkyl hydroperoxides (YOOH; dry methanol solvent, 30 degrees C) by heterolytic O-O bond scission that accompanies the transfer of an oxygen atom to the iron(III) moiety [(EDTA)Fe(III) + YOOH----[(EDTA)(FeO)]+ + YOH]. A single linear free-energy relationship exists for both peroxycarboxylic acids and alkyl hydroperoxides when the logarithm of the second-order rate constant (kYOOH) for reaction of YOOH species with (EDTA)Fe(III) is plotted vs. the pKa of the YOH leaving group.