A novel series of vanadium-sulfite polyoxometalates: synthesis, structural, and physical studies

Miras, H.N. , Raptis, R.G., Lalioti, N., Sigalas, M.P., Baran, P. and Kabanos, T.A. (2005) A novel series of vanadium-sulfite polyoxometalates: synthesis, structural, and physical studies. Chemistry: A European Journal, 11(8), pp. 2295-2306. (doi: 10.1002/chem.200400203)

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Abstract

Reaction of NH4VO3 with sulfur dioxide affords the hexanuclear cluster (NH4)(2)(Et4N)((VO)-O-IV)(6)(mu(4)-O)(2)(mu(3)-OH)(2)(mu(3)-SO3)(4)(H 2O)(2)]Cl center dot H2O (1), and the decapentanuclear host-guest compound (Et4N)(5){Cl subset of(VO)(15)(mu(3)-O)(18)(mu-O)(3)]}center dot 3H(2)O (2). Sequential addition of magnesium oxide to an acidic aqueous solution of NH4VO3 (pH approximate to 0) followed by (NH4)(2)SO3 resulted in the formation of either the non-oxo polymeric vanadium(IV) compound trans-(NH4)(2)V-IV(OH)(2)(mu-SO3)(2)] (3) or the polymeric oxovanadium(IV) sulfite (NH4)(VO)-O-IV-(SO3)(1.5)(H2O)]center dot 2.5 H2O (4) at pH values of 6 and 4, respectively. The decameric vanadium(v) compound {Na-4(mu-H2O)(8)(H2O)(6)} Mg(H2O)(6)]V-10(V)(O)(8)(mu(6)-O)(2)(mu(3)-O)(14)]center dot 3H(2)O (5) was synthesised by treating an acidic aqueous solution of NH4VO3 with MgO and addition of NaOH to pH approximate to 6. All the compounds were characterised by single-crystal Xray structure analysis. The crystal structure of compound I revealed an unprecedented structural motif of a cubane unit M-4(mu(4)-O)(2)(mu 3-OH)(2)] connected to two other metal atoms. Compound 3 comprises a rare example of a non-oxo vanadium(IV) species isolated from aqueous solution and in the presence of the reducing agent SO32-, while compound 4 represents a rare example of an open-framework species isolated at room temperature (20 degrees C). In addition to the synthesis and crystallographic studies, we report the IR and magnetic properties (for 1, 2 and 3) of these vanadium clusters as well as theoretical studies on compound 3.

Item Type:Articles
Additional Information:Symposium on Chemistry-A European Conference - Stimulating Concepts in Chemistry, Inst Sci Ingenierie Supramoleculaires, Strasbourg, FRANCE, APR 15, 2005.
Keywords:density functional calculations; polyoxometalates; structure elucidation; sulfites; vanadium
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Moiras, Professor Haralampos
Authors: Miras, H.N., Raptis, R.G., Lalioti, N., Sigalas, M.P., Baran, P., and Kabanos, T.A.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry: A European Journal
Journal Abbr.:Chem. Eur J.
ISSN:0947-6539
ISSN (Online):1521-3765
Published Online:01 February 2005

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