Synthesis and properties of isocyanate and isothiocyanate d1- and d2-complexes of vanadocene |
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| Institution: | 1. Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 – UCCS Unité de Catalyse et Chimie Solide, F-59000, Lille, France;2. Department of Chemistry, Center for Sustainable Chemistry, Ghent University, Krijgslaan 281 (S-3), 9000, Ghent, Belgium;1. Department of Chemistry, University of Puerto Rico Río Piedras, San Juan 00931, Puerto Rico;2. Department of Environmental Sciences, University of Puerto Rico Río Piedras, San Juan 00931, Puerto Rico |
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| Abstract: | The reactions of vanadocene and its halides Cp2VCl and Cp2VCl2 with R3MNCX (M Sn, Si, X O, S) and R2M(NCX)2 in various molar ratios have been studied. The reactions proceed either by an exchange of groups, with no change in the oxidation state of vanadium, or by an oxidative addition of pseudohalide ligand: VII → VIII; VIII → VIV. Oxidative addition results in the formation of (R3M)2 or gaseous hydrogen (in the reaction with HCl) in the reaction products.We have prepared the first ever monomeric and readily oxidisable d2-complexes of VIII of Cp2VNCX-type and asymmetric d1-complexes of Cp2V(Cl)NCX type, which, although rather stable in air, undergo disproportionation into symmetric d1-complexes on heating. In transmetallation reactions the ligand activity is found to increase in the order C1 < NCO < NCS. The complexes were characterised by GLC analysis, IR and ESR spectroscopy. A general scheme for the disproportionation reaction of asymmetric complexes of vanadocene is supported by differential thermal analysis data. |
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