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Updated: Jun 23, 2026
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Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model
Published on: May 23, 2018
Air oxidation of divanadium(IV) complexes.
Rune Kirk Egdal1, Andrew D Bond, Christine J McKenzie
1University of Southern Denmark, Department of Physics and Chemistry, Campusvej 55, 5230, Odense M, Denmark.
Dalton Transactions (Cambridge, England : 2003)
|May 7, 2009
Summary
Air oxidation of a dinuclear vanadium complex yields two distinct products. Reaction conditions, including solvent and concentration, influence product formation and reaction rates.
Area of Science:
- Inorganic Chemistry
- Oxidation Chemistry
- Coordination Chemistry
Background:
- Dinuclear vanadium complexes are of interest due to their diverse reactivity.
- The specific complex, [(V=O)2bpbp(OH2)2](ClO4)3.H2O, undergoes oxidation by atmospheric oxygen.
- Understanding the oxidation pathways is crucial for catalyst design and reaction control.
Purpose of the Study:
- To characterize the products of air oxidation of the dinuclear vanadium complex [(V=O)2bpbp(OH2)2](ClO4)3.H2O.
- To investigate the kinetics and solvent dependence of the oxidation reaction.
- To elucidate the mechanism of product formation, including transient species.
Main Methods:
- Solid-state characterization of oxidation products using techniques like X-ray crystallography.
- Kinetic studies to determine reaction rates and solvent effects.
- Spectroscopic detection of transient intermediates.
Main Results:
- Two distinct oxidation products were characterized: a V(V) diperoxido complex and a V(V)/V(IV) trioxido complex.
- The reaction rate is solvent-dependent, with 2-propanol yielding the fastest rate.
- A transient VV hydroperoxido species was detected, suggesting a complex reaction mechanism.
- Higher concentrations of the starting material favor the formation of one product over the other, likely via a bimolecular pathway.
Conclusions:
- The air oxidation of the dinuclear vanadium complex is a complex process yielding distinct V(V) and V(V)/V(IV) products.
- Reaction conditions significantly influence the outcome, with solvent and concentration being key factors.
- The proposed mechanism involves a transient hydroperoxido species and concentration-dependent pathways.
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