Tadatake Sato, H. Niino, A. Yabe
Jul 26, 2001
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Journal
Journal of Physical Chemistry A
Abstract
The generation of 1- and 2-naphthynes by the photolyses of 1,2- and 2,3-naphthalenedicarboxylic anhydrides (1, 2), respectively, was investigated by means of Fourier transformed infrared (FT-IR) and ultraviolet−visible (UV−Vis) absorption spectroscopies and theoretical calculations. Consecutive decarboxylation and decarbonylation of 1 were quantitatively analyzed on the basis of UV−Vis absorption spectra. The quantum efficiencies of these processes were estimated as 2 × 10-4 and 0.1, respectively. An isotopomer experiment showed that a cyclopropanone intermediate formed by the decarboxylation showed four CO stretching bands due to anharmonic resonance. Benzocyclopentadienylideneketene was formed from 1-naphthyne and CO, whereas 2-naphthyne did not react with CO to form the corresponding ketene. This different behavior was discussed on the basis of the geometries and energies calculated at the B3LYP/6-31G** level. Moreover, it was shown that the UV−Vis absorption spectra of reactive intermediates generated...