Reactions of Vanadium Dioxide Molecules with Acetylene:
Infrared Spectra of VO<sub>2</sub>(η<sup>2</sup>‑C<sub>2</sub>H<sub>2</sub>)<sub><i>x</i></sub> (<i>x</i> = 1, 2) and OV(OH)CCH in Solid Neon
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Abstract
Reactions
of vanadium dioxide molecules with acetylene have been
studied by matrix isolation infrared spectroscopy. Reaction intermediates
and products are identified on the basis of isotopic substitutions
as well as density functional frequency calculations. Ground state
vanadium dioxide molecule reacts with acetylene in forming the side-on-bonded
VO<sub>2</sub>(η<sup>2</sup>-C<sub>2</sub>H<sub>2</sub>) and
VO<sub>2</sub>(η<sup>2</sup>-C<sub>2</sub>H<sub>2</sub>)<sub>2</sub> complexes spontaneously on annealing in solid neon. The VO<sub>2</sub>(η<sup>2</sup>-C<sub>2</sub>H<sub>2</sub>) complex is
characterized to have a <sup>2</sup>B<sub>2</sub> ground state with <i>C</i><sub>2<i>v</i></sub> symmetry, whereas the VO<sub>2</sub>(η<sup>2</sup>-C<sub>2</sub>H<sub>2</sub>)<sub>2</sub> complex has a <sup>2</sup>A ground state with <i>C</i><sub>2</sub> symmetry. The VO<sub>2</sub>(η<sup>2</sup>-C<sub>2</sub>H<sub>2</sub>) and VO<sub>2</sub>(η<sup>2</sup>-C<sub>2</sub>H<sub>2</sub>)<sub>2</sub> complexes are photosensitive. The
VO<sub>2</sub>(η<sup>2</sup>-C<sub>2</sub>H<sub>2</sub>) complex
rearranges to the OV(OH)CCH molecule upon UV–vis light excitation
