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Kinetics and mechanism of the oxidation of butane‐2,3‐diol by alkaline hexacyanoferrate (III), catalyzed by ruthenium trichloride
Author(s) -
Balado A. Mucientes,
Jimenez F. Santiago,
Martín F. J. Poblete,
Castellanos R. Varón
Publication year - 1997
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1997)29:1<1::aid-kin1>3.0.co;2-y
Subject(s) - chemistry , disproportionation , ruthenium , butane , catalysis , kinetics , diol , rate determining step , substrate (aquarium) , ligand (biochemistry) , inorganic chemistry , reaction mechanism , photochemistry , medicinal chemistry , polymer chemistry , organic chemistry , biochemistry , physics , oceanography , receptor , quantum mechanics , geology
The kinetics of oxidation of butane‐2,3‐diol by alkaline hexacyanoferrate (III), catalyzed by ruthenium trichloride has been studied spectrophotometrically. The reaction rate shows a zero‐order dependence on oxidant, a first‐order dependence on |Ru(III)| T , a Michaelis‐Menten dependence on |diol|, and a variation complicated on |OH − |. A reaction mechanism involving the existence of two active especies of catalyst, Ru(OH) 2 + and Ru(OH) 3 , is proposed. Each one of the active species of catalyst forms an intermediate complex with the substrate, which disproportionates in the rate determining step. The complex disproportionation involves a hydrogen atom transfer from the α C(SINGLE BOND)H of alcohol to the oxygen of hydroxo ligand of ruthenium, to give Ru(II) and an intermediate radical which is then further oxidized. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 1–7, 1997.