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Unusual reaction of a tungsten alkylidyne complex with water. Formation, characterization, and crystal structures of oxo trimers

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Abstract

The reaction of the alkyl alkylidyne W(CH2CMe3)3(≡CSiMe3) (1) with H2O in THF and with D2O in benzene-d 6 gave two new trimeric oxo complexes: W3O3(µ=O)3(CH2CMe3)6(THF)3 (2) and [W3O3(µ=O)3(CH2CMe3)6(D2O)3]·2benzene-d 6 (3·2benzene-d 6), respectively, each containing two alkyl ligands per W atom. This is in contrast to the dimer W2O2(µ-O)(CH2CMe3)6, containing three alkyl ligands per W atom, from the previously reported reaction of the alkyl alkylidyne analog W(CH2CMe3)3-(≡CCMe3) with H2O. In the reaction of 1 with D2O in THF, an unstable intermediate W2O2(µ-O)(CD2SiMe3)2(CH2CMe3)4 (4-d 4) was identified. Kinetic studies of the reactions of 1 with excess H2O and D2O in THF-d 8, yielding 4 and 4-d 4, respectively, give a kinetic isotope effect (KIE) of 3.46(3) at 298(1) K, suggesting that the disappearance of 1 is a rate-determining step.

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  1. Department of Chemistry, University of Tennessee, Knoxville, Tennessee, 37996-1600, USA

    Brenda A. Dougan & Zi-Ling Xue

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Dougan, B.A., Xue, ZL. Unusual reaction of a tungsten alkylidyne complex with water. Formation, characterization, and crystal structures of oxo trimers. Sci. China Chem. 54, 1903–1908 (2011). https://doi.org/10.1007/s11426-011-4419-3

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