Oxovanadium(IV)-sulfite compounds: Synthesis and structural and physical studies

Chilas, G.I., Miras, H.N. , Manos, M.J., Woollins, J.D., Slawin, A.M.Z., Stylianou, M., Keramidas, A.D. and Kabanos, T.A. (2005) Oxovanadium(IV)-sulfite compounds: Synthesis and structural and physical studies. Pure and Applied Chemistry, 77(9), pp. 1529-1538. (doi: 10.1351/pac200577091529)

Abstract

Reaction of VIVOCl2 in strongly acidic aqueous solution with either (NH4)(2)SO3 or Na2SO3 and Bu4NBr at similar to 70 degrees C in the pH range 2.5-4.5 gives the clusters (NH4)(2){V-4(IV)(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO3)( 4)O-4(H2O)(2)} and (n-Bu4N)(2){V-4(IV)(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO 3)(4)O-4(H2O)(2)}, respectively. Reaction of (NH4VO3)-O-V with (NH4)(2)SO3 resulted in the isolation of the first compound. When the latter reaction is carried out in the presence of MgO, compound (NH4)(VO)-O-IV(SO3)(1.5)H2O](infinity)center dot 2.5H(2)O was isolated instead. Compound (n-Bu4N)(2){V-4(IV)(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO 3)(4)O-4(H2O)(2)} and (NH4)(VO)-O-IV(SO3)(1.5)H2O](infinity)center dot 2.5H(2)O were characterized by X-ray structure analysis. The crystal structure of species (n-Bu4N)(2){IV4IV(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO3)(4) O-4(H2O)(2)} revealed a unprecedented hexanuclear cluster consisting of a cubane core M-4(mu(4)-O)(2)(mu(3)- OH)(2)] connected to two other metal atoms through the core oxo-groups and four mu(3)-SO3 bridges. Compound (NH4)VIVO(SO3)(1.5)H2O](infinity)center dot 2.5H(2)O represents a rare example of an open-framework species prepared under mild conditions. Cyclic voltammetric examination of compound (n-Bu4N)(2){IV4IV(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO3) (4)O-4(H2O)(2)] revealed a redox process which was assigned to the oxidation of one core of vanadium(IV) to vanadium(V).

• Item Type: Articles
• Additional Information: 4th International Symposium on Chemistry and Biological Chemistry of Vanadium, Szeged, HUNGARY, SEP 03-05, 2004
• Keywords: oxovanadium, sulfite, vanadium clusters, vanadium(IV), electrochemistry
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Moiras, Professor Haralampos
• Authors: Chilas, G.I., Miras, H.N., Manos, M.J., Woollins, J.D., Slawin, A.M.Z., Stylianou, M., Keramidas, A.D., and Kabanos, T.A.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Pure and Applied Chemistry
• Journal Abbr.: Pure Appl. Chem.
• ISSN: 0033-4545
• ISSN (Online): 1365-3075