The Influence of Steric Effects on the Oxidation Kinetics of [FeII(aminopolycarboxylato)] Complexes with Dioxygen
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Sabine Seibig
Abstract
The oxidation kinetics for the reaction of [FeII(1,2- pdta)] (1,2-pdta = 1,2-N,N′-1,2-propylenediaminetetraacetate) and [FeII(1,3-pdta)] (1,3-pdta = 1,2-N,Ν′- 1,3-propylenediaminetetraacetate) with molecular oxygen were studied as a function of [FeII], [O2], pH, temperature and pressure. It was observed that the reaction with [FeII(1,2-pdta)] is ca. 200 times faster than with the isomeric [FeII(1,3-pdta)] complex under comparable conditions. In the presence of an excess of [FeII(1,2-pdta)] three reaction steps could be identified for which the rate constants are = 3385 ± 607M-1 s-1, k2 = 226±9M-1s-1 and k3 = 111 ± 4M-1s-1 at pH = 6 and T = 25°C. Since [FeII(1,3-pdta)] is unstable during the reaction, only approximate rate constants for two of the electron-transfer steps could be determined, which are two orders of magnitude smaller than in the case of the [FeII(1,2-pdta)] complex. Rate and activation parameters for the 1,2-pdta system are reported and discussed in reference to our earlier work on related systems.
© 2014 by Walter de Gruyter Berlin/Boston
Artikel in diesem Heft
- Tribute
- Kinetics of Dissociation of the Cobalt(II) and Copper(II) Complexes of 2,2′,2″-tris(monomethylamino)triethylamine in Aqueous Acidic Solution
- The Influence of Steric Effects on the Oxidation Kinetics of [FeII(aminopolycarboxylato)] Complexes with Dioxygen
- The Hydrolysis Kinetics of ds-diamminedichloroplatinum(II). 10. Activation Volumes for Halide Anation of Some czs-[Pt(N)2(OH2)2]2+ Systems
- The Dependence of the Copper Dissociation Rate Constants from Human(Serum)- and Ονο-Transferrin on pH and the Anions
- Kinetics of the Photosubstitution of ds-Bis(benzonitrile)dichloroplatinum(II) in Chloroform
- Kinetics and Mechanisms of the Reaction of Aluminium(III) with Polyaminocarboxylic Acids
- Kinetics and Mechanism of Oxidation of Tellurium(IV) by Alkaline Diperiodatonickelate(IV)
- Complexation of Pendant Arm Macrocycles with Cu(II) Hydroxo Complexes in Strongly Alkaline Solutions. Investigation of pH Dependences
- Kinetics and Mechanism of the Chromium(VI) Oxidation of Formic Acid in the Presence of Picolinic Acid and in the Presence and Absence of Surfactants
- Kinetics and Mechanism of Chromium(III) Catalysed Oxidation of Propan-1-ol and Butan-1-ol by Cerium(IV) in Aqueous Sulfuric acid Media
- Notes for Contributors. Inorganic Reaction Mechanisms
- Journal Order Form
Artikel in diesem Heft
- Tribute
- Kinetics of Dissociation of the Cobalt(II) and Copper(II) Complexes of 2,2′,2″-tris(monomethylamino)triethylamine in Aqueous Acidic Solution
- The Influence of Steric Effects on the Oxidation Kinetics of [FeII(aminopolycarboxylato)] Complexes with Dioxygen
- The Hydrolysis Kinetics of ds-diamminedichloroplatinum(II). 10. Activation Volumes for Halide Anation of Some czs-[Pt(N)2(OH2)2]2+ Systems
- The Dependence of the Copper Dissociation Rate Constants from Human(Serum)- and Ονο-Transferrin on pH and the Anions
- Kinetics of the Photosubstitution of ds-Bis(benzonitrile)dichloroplatinum(II) in Chloroform
- Kinetics and Mechanisms of the Reaction of Aluminium(III) with Polyaminocarboxylic Acids
- Kinetics and Mechanism of Oxidation of Tellurium(IV) by Alkaline Diperiodatonickelate(IV)
- Complexation of Pendant Arm Macrocycles with Cu(II) Hydroxo Complexes in Strongly Alkaline Solutions. Investigation of pH Dependences
- Kinetics and Mechanism of the Chromium(VI) Oxidation of Formic Acid in the Presence of Picolinic Acid and in the Presence and Absence of Surfactants
- Kinetics and Mechanism of Chromium(III) Catalysed Oxidation of Propan-1-ol and Butan-1-ol by Cerium(IV) in Aqueous Sulfuric acid Media
- Notes for Contributors. Inorganic Reaction Mechanisms
- Journal Order Form
