J. Grzegorzek, Z. Mielke
FULL PAPER
tained results also suggest that in solution the photolytic
conversion of the syn1 and syn3 conformers (with and with-
out intramolecular hydrogen bond) into benzoxazole may
occur by the same mechanism of phenolate ion formation.
However, in the case of the syn1 conformer with the intra-
molecular hydrogen bond, a first step of an overall reaction
is syn1Ǟsyn3 conversion.
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The partially deuterated [D
solving salicylaldoxime in D
2
]salicylaldoxime was obtained by dis-
O and evaporating the heavy water,
2
the procedure was repeated three times. The matrices were prepared
in the same way as for the nondeuterated sample. The infrared
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cooled by liquid N .
Computational Methods: Optimization of all the structures as well
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to optimize the structures of salicylaldoxime conformers however
only the harmonic frequencies were calculated by the MP2 method.
For all energies the zero-point energy values have been considered.
All the stationary points were unambiguously characterized as mi-
nima or transition states by their vibrational spectra. To investigate
the effects of a polar environment on the structure and energetics
of the salicylaldoxime conformers the Conductor-like Polarizable
Continuum Model (CPCM) at the B3LYP/6-311++G(2d,2p) levels
was applied. A potential energy distribution (PED) of the normal
modes was computed in terms of natural internal coordinates with
the Gar2ped program.[
[
6
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2
-cyanophenol–H
for all optimized salicylaldoxime conformers and all optimized 2-
cyanophenol–H O complexes; experimental infrared spectra of
]salicylaldoxime matrices; selected structural parameters and
comparison of experimental frequencies with theoretical ones for
the 3 salicylaldoxime and [D ]salicylaldoxime conformers and 2 2-
cyanophenol–H O and 2-[D ]cyanophenol–HDO complexes iden-
tified in the present study.
2
O complexes; calculated vibrational frequencies
2
[D
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