Reaction of NH4VO3 with sulfur dioxide affords the hexanuclear cluster (NH4)2(Et4N)[(VIVO)6(μ4‐O)2(μ3‐OH)2(μ3‐SO3)4(H2O)2]Cl⋅H2O (1), and the decapentanuclear host–guest compound (Et4N)5{Cl⊂ [(VO)15(μ3‐O)18(μ‐O)3]}⋅3 H2O (2). Sequential addition of magnesium oxide to an acidic aqueous solution of NH4VO3 (pH≈0) followed by (NH4)2SO3 resulted in the formation of either the non‐oxo polymeric vanadium(IV) compound trans‐(NH4)2[VIV(OH)2(μ‐SO3)2] (3) or the polymeric oxovanadium(IV) sulfite (NH4)[VIVO(SO3)1.5(H2O)]⋅2.5 H2O (4) at pH values of 6 and 4, respectively. The decameric vanadium(V) compound {Na4(μ‐H2O)8(H2O)6}[Mg(H2O)6][V${{{{\rm V}\hfill \atop 10\hfill}}}$(O)8(μ6‐O)2(μ3‐O)14]⋅3 H2O (5) was synthesised by treating an acidic aqueous solution of NH4VO3 with MgO and addition of NaOH to pH≈6. All the compounds were characterised by single‐crystal X‐ray structure analysis. The crystal structure of compound 1 revealed an unprecedented structural motif of a cubane unit [M4(μ4‐O)2(μ3‐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 °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.

A varied family of vanadium(IV) sulfite compounds comprising, for example the hexanuclear [H2${{{\rm {\rm V}}{{{\rm {\rm IV}}\hfill \atop 6\hfill}}}}$O10(μ3‐SO3)4(H2O)2]2− cluster, which exhibits a unique structural motif (I), the non‐oxovanadium(IV) sulfite species trans‐[VIV(OH)2(μ‐SO3)]2− (II), and the oxovanadium(IV) sulfite species [VIVO(SO3)1.5H2O]−, has been synthesised and characterised.

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{{Explor lien
   |wiki=    Sante
   |area=    H2N2V1
   |flux=    Main
   |étape=   Exploration
   |type=    RBID
   |clé=     ISTEX:D4F29D598D52DE502DA628392064E6AF2D154090
   |texte=   A Novel Series of Vanadium‐Sulfite Polyoxometalates: Synthesis, Structural, and Physical Studies
}}