Reactivity and structure of the 5-dehydro-m-xylylene anion.
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 (1a), consistent with theoretical predictions. Density functional calculations predict a nonplanar 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.
Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084, USA.
Tamara E
TE
Munsch
Lyudmila V
LV
Slipchenko
Anna I
AI
Krylov
Paul G
PG
Wenthold