Reactivity and Structure of the 5-Dehydro-m-xylylene Anion

T. E. Munsch, L. V. Slipchenko, A. I. Krylov, and P. G. Wenthold
J. Org. Chem. 69, 5735 – 5741 (2004)

The electronic structure of dehydro-m-xylylene anion (DMX^-) has been investigated by using chemical reactivity studies and electronic structure calculations. DMX^- has been generated in the gas phase via the sequential reaction of trimethyl-3,5-bis(trimethylsilylmethyl)phenylsilane with F^- and two molecules of F₂. Reactivity and thermochemical properties of the ion indicate a phenyl-like anion, consistent with theoretical predictions. Calculations indicate a non-planar triplet anion, with an allenic singlet anion slightly higher in energy. The driving force for the out-of-plane distortion is more efficient charge delocalization that is achieved at lower symmetry.

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