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Red crystals, isolated from a highly concentrated methanol solution of the trimeric complex, were analysed by X\u2010ray crystallography. The solid\u2010state structure of the compound showed the presence of a new dinuclear V<jats:sup>V<\/jats:sup> cluster and allowed for its formulation as a [V<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub>(\u03bc\u2010O)(dmpp)<jats:sub>2<\/jats:sub>(OCH<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>] complex, V<jats:sub>2<\/jats:sub>Y<jats:sub>2<\/jats:sub>L<jats:sub>2<\/jats:sub> (Y = OCH<jats:sub>3<\/jats:sub>). This complex crystallises in the monoclinic system: <jats:italic>P<\/jats:italic>2<jats:sub>1<\/jats:sub>\/<jats:italic>c<\/jats:italic>, <jats:italic>a<\/jats:italic> = 8.4573(11) \u00c5, <jats:italic>b<\/jats:italic> = 15.034(2) \u00c5 and <jats:italic>c<\/jats:italic> = 15.849(2) \u00c5, <jats:italic>\u03b2<\/jats:italic> = 105.300(2)\u00b0, <jats:italic>V<\/jats:italic> = 1943,7(4) \u00c5<jats:sup>3<\/jats:sup>, <jats:italic>Z<\/jats:italic> = 2, and <jats:italic>R<\/jats:italic><jats:sub>1<\/jats:sub>(<jats:italic>wR<\/jats:italic><jats:sub>2<\/jats:sub>) = 0.0492(0.1706). The trimer V<jats:sub>3<\/jats:sub>L<jats:sub>3<\/jats:sub> complex dissolved in a dry methanol solution fully decomposes, as shown by the <jats:sup>51<\/jats:sup>V NMR signals at \u2013388, \u2013450 and \u2013551 ppm, which are assigned to a monomer complex [VO(OMe)(dmpp)<jats:sub>2<\/jats:sub>] (VYL<jats:sub>2<\/jats:sub>), the dimer V<jats:sub>2<\/jats:sub>Y<jats:sub>2<\/jats:sub>L<jats:sub>2<\/jats:sub> and the monomethyl ester of monovanadate, V<jats:sub>1<\/jats:sub>Y (V<jats:sub>1<\/jats:sub> = monovanadate; Y = OCH<jats:sub>3<\/jats:sub>), respectively. In methanol\/water solutions, a new <jats:sup>51<\/jats:sup>V NMR signal appears at <jats:italic>\u03b4<\/jats:italic> = \u2013492 ppm, which is assigned to the [VO<jats:sub>2<\/jats:sub>(dmpp)(H<jats:sub>2<\/jats:sub>O)<jats:sub>2<\/jats:sub>] (VL) complex. When the percentage of water in the mixture increases, the relative intensities of the V<jats:sub>2<\/jats:sub>Y<jats:sub>2<\/jats:sub>L<jats:sub>2<\/jats:sub> and V<jats:sub>1<\/jats:sub>Y signals decrease sharply, and a broad signal at \u2013488 ppm appears, corresponding to the original V<jats:sup>V<\/jats:sup> trimer complex, which is the only species present in 94\u2009% water. A temperature\u2010dependent <jats:sup>1<\/jats:sup>H NMR study of a CD<jats:sub>3<\/jats:sub>OD solution of V<jats:sub>3<\/jats:sub>L<jats:sub>3<\/jats:sub> confirmed the presence, at room temperature, of the dinuclear V<jats:sub>2<\/jats:sub>L<jats:sub>2<\/jats:sub> complex and the VL<jats:sub>2<\/jats:sub> species. At temperatures below 0 \u00b0C down to \u201350 \u00b0C, the appearance of new signals reflects the presence of isomers for the V<jats:sub>2<\/jats:sub>Y<jats:sub>2<\/jats:sub>L<jats:sub>2<\/jats:sub> and VYL<jats:sub>2<\/jats:sub> species with different stabilities and symmetries. 2D <jats:sup>1<\/jats:sup>H homonuclear NMR exchange experiments (EXSY) allowed us to establish the isomeric equilibria that take place in solution, and indicates intramolecular exchange between the two ligands of the major isomer of VYL<jats:sub>2<\/jats:sub> and intermolecular exchange between the major and minor isomers of species of different nuclearity, V<jats:sub>2<\/jats:sub>Y<jats:sub>2<\/jats:sub>L<jats:sub>2<\/jats:sub> and VYL<jats:sub>2<\/jats:sub>. However, no evidence was found for intermolecular exchange between the major isomers and between the minor isomers of species of different nuclearity or between isomers of species of the same nuclearity. (\u00a9 Wiley\u2010VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2006)<\/jats:p>","DOI":"10.1002\/ejic.200600301","type":"journal-article","created":{"date-parts":[[2006,7,24]],"date-time":"2006-07-24T10:19:08Z","timestamp":1153736348000},"page":"3586-3594","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Crystal Structure of the V<sup>V<\/sup> Dimer [V<sub>2<\/sub>O<sub>2<\/sub>(\u03bc\u2010O)(dmpp)<sub>2<\/sub>(OCH<sub>3<\/sub>)<sub>2<\/sub>] and Its Equilibrium with the V<sup>V<\/sup> Trimer [V<sub>3<\/sub>O<sub>3<\/sub>(\u03bc\u2010O)<sub>3<\/sub>(dmpp)<sub>3<\/sub>(H<sub>2<\/sub>O)](H<sub>2<\/sub>O)<sub>2<\/sub> in Methanol\/Water Solutions"],"prefix":"10.1002","volume":"2006","author":[{"given":"Fernando","family":"Avecilla","sequence":"first","affiliation":[]},{"given":"Carlos F. G. C.","family":"Geraldes","sequence":"additional","affiliation":[]},{"given":"Anjos L.","family":"Macedo","sequence":"additional","affiliation":[]},{"given":"M. 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