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Synthesis and characterisation of new binuclear oxo-vanadium(IV) complexes with a bis(bidentate)oxalate bridge. Crystal structures of the cationic and anionic complexes

Abstract : The new oxalate - vanadyl compounds [V2O2(C2O4)(H2O)6]Cl2 4Bu4NCl H2O (1) (Bu=C4H9) and [Et4N]4[V2O2(C2O4)(NCS)6] (2') (Et = C2H5) have been synthesized starting from V2O5 and VOSO4 5H2O, respectively. Metathesis of 2' with [FeCp2*]BF4 (Cp* = CS(CH3)5) gave a partial substitution of the cations affording FeCp2*]2[Et4N]2[V2O2(C2O4)(NCS)6] (2). The X-ray structures of 1 and 2 have been determined. In both complexes, which crystallise in the monoclinic space group P21/c, the centrosymmetric binuclear vanadium species present a bis(bidentate)oxalate ligand and an almost planar [V2O2(C2O4)X2] unit (X = O(H2O) for 1 and N(NSC) for 2)with two V = O groups located in trans positions in the equatorial plane. In both cases, the strong V = O terminal bond (1.569(7) in 1, 1,580(7) Å in 2) has a strong trans influence which is slightly greater in the cation of I than in the anion of 2. Magnetic susceptibility measurements indicate weak antiferromagnetic pairwise interactions for 1, 2 and 2'. (C) 2000 Elsevier Science S.A.
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Submitted on : Thursday, April 19, 2018 - 2:49:21 PM
Last modification on : Monday, October 11, 2021 - 2:22:08 PM

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Smail Triki, F. Bérézovsky, J. Sala Pala, M.-T. Garland. Synthesis and characterisation of new binuclear oxo-vanadium(IV) complexes with a bis(bidentate)oxalate bridge. Crystal structures of the cationic and anionic complexes. Inorganica Chimica Acta, Elsevier, 2000, 308, pp.31--36. ⟨10.1016/S0020-1693(00)00192-4⟩. ⟨hal-01771385⟩

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