Oxidation of Thioglycolic Acid by Nickel(IV) Oxime-Imine Complexes - A Kinetic and Mechanistic Approach
-
Santanu Bhattacharya
Abstract
The kinetics of oxidation of thioglycolic acid (H2A) by two nickel(IV) oxime-imine complexes, [NiIV(L1)2]2 + and [NiIV(L2)]2+ (where HL1 and H2L2 are 6-amino-3-methyl-4-azahex-3-ene-2-one oxime and 3,14-dimethyl-4,7,10,13-tetraazahexadeca-3,13- diene-2,15-dione dioxime respectively) were carried out by using stopped-flow technique in the pH range 3.0-8.0. Under pseudo-first-order conditions the reaction follows a general rate law: - (d/dt) [Ni(Lx)] =kobs [Ni(Lx)] = nk [Ni(Lx)] [H2A]T where n is the stoichiometric factor with 0.5 for NiIV → NIII reactions and 1 for each step of Ni IV→ NiIII → NiII biphasic conversions. The evaluation of rate and equilibrium constants of the reactants was achieved by employing suitable computer-fit programs. Both the reactions have been proposed to follow the inner-sphere mechanism through the formation of an associated species involving the sulfur atom of the thiol and the metal center of the oxidant.
© 2014 by Walter de Gruyter Berlin/Boston
Artikel in diesem Heft
- Editorial
- Dedicated to Ralph G. Wilkins
- Kinetic Studies of Water Exchange and Substitution by NCS– on the Sulphur-capped Triangular Ion [Μο3(μ3-S)(μ-O)3(ΟΗ2)9]4+
- A Kinetic Study of the Photolysis of Ethylferrocene in Chloroform
- Oxidation of Thioglycolic Acid by Nickel(IV) Oxime-Imine Complexes - A Kinetic and Mechanistic Approach
- The Copper(II)-2,2′-Dipyridylamine Catalysed Hydrolysis of the Phosphotriester 2,4-Dinitrophenyl Diethyl Phosphate and O-isopropyl Methylfluorophosphonate (Sarin)
- Oxidation of Thiol-containing Substrates by the Pentaamminechromatocobalt(III) Complex Ion
- Complex Formation of Iron(II/III) with [15]aneN4 in Aqueous Solution. Kinetics of the Oxidation of FeII([15]aneN4) by Dioxygen
- Hydrogen Atom Abstraction by Methyl Radicals from tert-Butyl Hydroperoxide in a Modified Fenton Reaction
- The Rate of Electron Self-Exchange in the System [CuIL]+/[CuIIL]2+ with L = 2,2′-Bis(3-(2-pyridyl)-l-methyltriazolyl)biphenyl
- Notes for Contributors Inorganic Reaction Mechanisms
- Disk Specifications
- Journal Order Form
Artikel in diesem Heft
- Editorial
- Dedicated to Ralph G. Wilkins
- Kinetic Studies of Water Exchange and Substitution by NCS– on the Sulphur-capped Triangular Ion [Μο3(μ3-S)(μ-O)3(ΟΗ2)9]4+
- A Kinetic Study of the Photolysis of Ethylferrocene in Chloroform
- Oxidation of Thioglycolic Acid by Nickel(IV) Oxime-Imine Complexes - A Kinetic and Mechanistic Approach
- The Copper(II)-2,2′-Dipyridylamine Catalysed Hydrolysis of the Phosphotriester 2,4-Dinitrophenyl Diethyl Phosphate and O-isopropyl Methylfluorophosphonate (Sarin)
- Oxidation of Thiol-containing Substrates by the Pentaamminechromatocobalt(III) Complex Ion
- Complex Formation of Iron(II/III) with [15]aneN4 in Aqueous Solution. Kinetics of the Oxidation of FeII([15]aneN4) by Dioxygen
- Hydrogen Atom Abstraction by Methyl Radicals from tert-Butyl Hydroperoxide in a Modified Fenton Reaction
- The Rate of Electron Self-Exchange in the System [CuIL]+/[CuIIL]2+ with L = 2,2′-Bis(3-(2-pyridyl)-l-methyltriazolyl)biphenyl
- Notes for Contributors Inorganic Reaction Mechanisms
- Disk Specifications
- Journal Order Form
