Conformational isomerization of 5-phenyl-1-pentene probed by SEP-population transfer spectroscopy.
Stimulated emission pumping-population transfer (SEP-PT) spectroscopy is used to experimentally determine upper and lower bounds on the energy thresholds to conformational isomerization between 14 X-->Y reactant-product conformer pairs of isolated 5-phenyl-1-pentene (5PPene). This work builds directly on the spectroscopic assignments of the five observed conformers of 5PPene in the preceding paper. The observed thresholds fall into two energy ranges: near 600 cm(-1) for isomerization processes that involve only reorientation of the terminal vinyl group, and in the 1200-1374 cm(-1) range for barriers that involve hindered rotation about the alkyl chain carbon-carbon bonds. As a result, this latter threshold opens up much of the conformational phase space to exploration, with multiple isomerization pathways connecting any two of the conformational minima.
Pillsbury
Nathan R
NR
Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907, USA.
Zwier
Timothy S
TS