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DOI: 10.1039/A602941H (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 93-98

Synthesis of [W(η5-C5H5)2H(L)] and [W(η5-C5H5)2L2] 2+ cations (L = NCMe, NCPh, C4H8O or CNBut). Crystal and molecular structures of [W(η5-C5H5)2H(C4 H8O)][CF3SO3] and [W(η5-C5H5)2(NCMe)2 ][CF3SO3]2

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Adrian J. Carmichael and Andrew McCamley

Abstract

The cationic hydride complexes [W(η-C5H5)2H(L)][CF3SO 3] [L = NCMe, NCPh, tetrahydrofuran (thf) or CNBut] have been synthesized by reaction of [W(η-C5H5)2H2] and methyl trifluoromethanesulfonate in the presence of the σ-donor ligand L. Kinetic measurements on ligand-substitution reactions in CD3CN solution indicate that L is labile in solution; [W(η-C5H5)2H(L)]+ cations have half-lives of 315(10), 122(6) and 6.68(5) h (L = NCMe, NCPh or thf respectively) at 44 °C. The activation energy Ea for tetrahydrofuran substitution in [W(η-C5H5)2H(thf)]+ is 132 ± 1 kJ mol-1. An X-ray crystallographic determination of the structure of [W(η-C5H5)2H(thf)][CF3SO 3] demonstrates that the tetrahydrofuran ligand is oriented ‘in-plane’ with the centroid–W–centroid plane, indicating that the thf acts as a simple σ-donor ligand. Reaction of [W(η-C5H5)2H2] with an excess of CF3SO3Me yields the dicationic tungstenocene complex [W(η-C5H5)2(NCMe)2][CF 3SO3]2 as demonstrated by IR and NMR spectroscopy and X-ray crystallography.

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