4.7 Article

Reactivity of niobium and tantalum pentahalides with cyclic ethers and the isolation and characterization of intermediates in the polymerization of tetrahydrofuran

Journal

INORGANIC CHEMISTRY
Volume 47, Issue 1, Pages 365-372

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ic7012254

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The complexes MX5(THF) (M = Nb, X = Cl, 2a; M = Ta, X = F, 2c, X = Cl, 2d) and [MX4(THF){O(CH2)(4)- [GRAPHICS] O(CH2)(3)CH2)}][MX6] (M = Nb, X = Cl, 3a; M = Ta, X = Cl, 3d, X = Br, 3e, X = l, 3f) result from reactions of MX5 with 0.5 and 1.5 equiv of THF, respectively. Compounds 3 contain the unprecedented 4-(tetrahydrofuran-1-ium)-butan-1-oxo ligand and are likely to play a role in the course of THF polymerization catalyzed by MX5. The addition of L (L = 2,5-dimethyltetrahydrofuran, tetrahydropyran, 1,4-dioxane) to MX5 results in the formation of the hexacoordinated complexes MX5(L). The molecular structures of 2d, 3d, and NbCl5(dioxane), 6a, have been ascertained by X-ray diffraction studies,

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