Spectral Investigation of Stability of the Peroxo Complexes M2[V2O2(O2)4H2O] . aq (M = N(CH3)4, N(C4H9)4) in Solutions

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Title:Spectral Investigation of Stability of the Peroxo Complexes M2[V2O2(O2)4H2O] . aq (M = N(CH3)4, N(C4H9)4) in Solutions
Creators:
Schwendt, Peter
Liščák, Karol
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 61, 6, pp. 868-876
Uncontrolled Keywords:Asymmetric tetraperoxodivanadate, IR spectroscopy, Solution stability, Electron spectroscopy

Abstract

Infrared spectra of solutions of M<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>H<sub>2</sub>O] . aq (M = N(CH<sub>3</sub>)<sub>4</sub>, N(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>) in heavy water and acetonitrile indicate that in concentrated solutions (<i>c</i> >= 0.5 mol dm<sup>-3</sup>) the asymmetric structure of the [V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>H<sub>2</sub>O]<sup>2-</sup> anion remains preserved for some time. Electronic spectra suggest that in more dilute solutions (<i>c</i> = 10<sup>-3</sup>-10<sup>-4</sup> mol dm<sup>-3</sup>) of the M<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>H<sub>2</sub>O] . aq complexes in water and acetonitrile the dinuclear ion decomposes faster to [VO(O<sub>2</sub>)<sub>2</sub>H<sub>2</sub>O]<sup>-</sup>, followed by a relatively slow liberation of the peroxidic oxygen and formation of vanadate ions. The dinuclear complex is more stable in dilute chloroform solutions. The <sup>51</sup>V NMR spectrum of an aqueous solution of [N(CH<sub>3</sub>)<sub>4</sub>]<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>H<sub>2</sub>O] (c = 1.3 mol dm<sup>-3</sup>) taken after a partial decomposition suggests the simultaneous presence of [V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>H<sub>2</sub>O]<sup>2-</sup>, [VO(O<sub>2</sub>)<sub>2</sub>H<sub>2</sub>O]<sup>-</sup>, (<i>V</i><sub><i>n</i></sub>O<sub>3<i>n</i></sub>)<sup><i>n</i>-</sup> (<i>n</i> = 4, 5, 6), [H<sub><i>m</i></sub>V<sub>10</sub>O<sub>28</sub>]<sup>(6-<i>m</i>)-</sup>, and other unidentified species.

Title:Spectral Investigation of Stability of the Peroxo Complexes M2[V2O2(O2)4H2O] . aq (M = N(CH3)4, N(C4H9)4) in Solutions
Creators:
Schwendt, Peter
Liščák, Karol
Uncontrolled Keywords:Asymmetric tetraperoxodivanadate, IR spectroscopy, Solution stability, Electron spectroscopy
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:6
Page Range:pp. 868-876
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19960868UNSPECIFIED
ID Code:988
Item Type:Article
Deposited On:06 Feb 2009 17:05
Last Modified:06 Feb 2009 16:05

Citation

Schwendt, Peter; Liščák, Karol (1996) Spectral Investigation of Stability of the Peroxo Complexes M2[V2O2(O2)4H2O] . aq (M = N(CH3)4, N(C4H9)4) in Solutions. Collection of Czechoslovak Chemical Communications, 61 (6). pp. 868-876. ISSN 0010-0765

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