Kinetics and mechanism of the vanadium(IV) oxidation of the (hydroxymethyl)chromium(III) ion

Journal Article · Fri May 01 04:00:00 EDT 1981 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50219a061· OSTI ID:6591583

Bakac, A; Espenson, J H

The oxidation of the (hydroxymethyl)chromium(III) ion by VO/sup 2 +/ was investigated in order to obtain more information about the mechanism(s) of oxidation of this type of chromium complexes. Arguments about the detailed mechanism of the inner-sphere oxidation of CrCH/sub 2/OH/sup 2 +/ by VO/sup 2 +/ are based mainly on the acidity dependence of the reaction rates. This approach, although very useful, has limitation, especially for the reactions of metal ions in higher oxidation states where the hydrolysis of the reactants and/or products may obscure the mechanistic picture. However even with that limitation the results of this work support the idea that CrCH/sub 2/OH/sup 2 +/ (and other (..cap alpha..-hydroxyalkyl)chromium complexes) preferably react with oxidants in inner-sphere reactions, most likely by forming bridged activated complexes through the alcoholic OH group.

• Research Organization: Ames Lab., IA
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6591583
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 20:5; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
CHROMIUM COMPLEXES
COMPLEXES
HALOGEN COMPOUNDS
HYDROXY COMPOUNDS
KINETICS
MEDIUM TEMPERATURE
ORGANIC COMPOUNDS
OXIDATION
OXYGEN COMPOUNDS
PERCHLORATES
REACTION INTERMEDIATES
REACTION KINETICS
SPECTROPHOTOMETRY
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
VANADIUM COMPOUNDS