Kinetic Study of Oxygen Transfer Reactions from Oxo-Monoperoxo Complexes of Vanadium(V) to Thiolatocobalt(III) Complex in Water and Concentrated Solutions of Electrolytes

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Title:Kinetic Study of Oxygen Transfer Reactions from Oxo-Monoperoxo Complexes of Vanadium(V) to Thiolatocobalt(III) Complex in Water and Concentrated Solutions of Electrolytes
Creators:
Vollárová, Oľga
Benko, Ján
Sivák, Michal
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 61, 4, pp. 574-588
Uncontrolled Keywords:Salt effect, Oxygen transfer reaction, Oxo-monoperoxo complexes of vanadium(V)

Abstract

[Co(en)<sub>2</sub>SCH<sub>2</sub>CH<sub>2</sub>NH<sub>2</sub>]<sup>2+</sup> ion is oxidized to [Co(en)<sub>2</sub>SOCH<sub>2</sub>CH<sub>2</sub>NH<sub>2</sub>]<sup>2+ </sup>by the oxo-monoperoxovanadium(V) complexes in aqueous media. These reactions are accompanied by oxygen atom transfer from the peroxo ligand to the coordinated sulfur atom. The relative reactivities for each substrate stand in the order: [VO(O<sub>2</sub>)(ada)]<sup>-</sup> &lt;&lt; [VO(O<sub>2</sub>)nta]<sup>2-</sup> ~ H<sub>2</sub>O<sub>2</sub> ~ [VO(O<sub>2</sub>)(H<sub>2</sub>O)<sub>4</sub>]<sup>+</sup> &lt; [VO(O<sub>2</sub>)(quin)<sub>2</sub>]<sup>3-</sup> &lt;&lt; [VO(O<sub>2</sub>)(H<sub>2</sub>O)<sub>2</sub>(pic)], where ada = <i>N</i>-(carbamoylmethyl)iminodiacetato(2-), nta = nitrilotriacetato(3-), quin = 2,3-pyridinedicarboxylato(2-) and pic = 2-pyridinecarboxylato(1-) ligands. The effect of pH on the second order rate constant for oxidation by monoperoxo-nta complex is in the pH range 4.8-6.5 consistent with equation <i>k</i>(298.2 K) = 0.709 + 1.28 . 10<sup>5 </sup>[H<sup>+</sup>]. Two new oxo-monoperoxo complexes of vanadium(V), NH<sub>4</sub>[VO(O<sub>2</sub>)(ada)] . H<sub>2</sub>O and (NH<sub>4</sub>)<sub>3</sub>[VO(O<sub>2</sub>)(quin)<sub>2</sub>] . 3 H<sub>2</sub>O, were synthesized and characterized. The salt effects on the thiolatocobalt(III) oxidation by vanadium(V) oxo-monoperoxo complexes as well as by H<sub>2</sub>O<sub>2 </sub>were studied at 298.2 K in different, up to 5 M solutions of electrolytes. The results can be rationalized in terms of the salt-water interactions.

Title:Kinetic Study of Oxygen Transfer Reactions from Oxo-Monoperoxo Complexes of Vanadium(V) to Thiolatocobalt(III) Complex in Water and Concentrated Solutions of Electrolytes
Creators:
Vollárová, Oľga
Benko, Ján
Sivák, Michal
Uncontrolled Keywords:Salt effect, Oxygen transfer reaction, Oxo-monoperoxo complexes of vanadium(V)
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:61
Number:4
Page Range:pp. 574-588
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19960574UNSPECIFIED
ID Code:957
Item Type:Article
Deposited On:06 Feb 2009 17:05
Last Modified:06 Feb 2009 16:05

Citation

Vollárová, Oľga; Benko, Ján; Sivák, Michal (1996) Kinetic Study of Oxygen Transfer Reactions from Oxo-Monoperoxo Complexes of Vanadium(V) to Thiolatocobalt(III) Complex in Water and Concentrated Solutions of Electrolytes. Collection of Czechoslovak Chemical Communications, 61 (4). pp. 574-588. ISSN 0010-0765

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