Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 131, Issue 37, Pages 13423-13429Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja904521c
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Funding
- Australian Research Councils Discovery funding scheme [PP0665831, DP0985767]
- University of Sydney
- Australian Government
- Australian Research Council
- Australian Research Council [DP0985767] Funding Source: Australian Research Council
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The cis-1-vinylpropargyl (cis-1VPR, cis-pent-4-en-1-yn-3-yl) and trans-1-vinylpropargyl (trans-1VPR, trans-pent-4-en-1-yn-3-yl) radicals, produced in a supersonically cooled hydrocarbon discharge, have been identified by a synergy of 2-dimensional fluorescence and ionization spectroscopies, revealing their electronic origin transitions at 21 232 and 21 645 cm(-1) respectively. These assignments are supported by an excellent agreement between calculated ground state frequencies of cis-1VPR and trans-1VPR with those obtained by dispersed fluorescence spectroscopy. in addition, high-resolution rotational contours of the two bands are well simulated using calculated (X) over tilde and (A) over tilde -state trans-1VPR and cis-1VPR rotational constants. Finally, computed origin transition energies of these two isomers are within several hundred wavenumbers of the observed band positions. With the 1-phenylpropargyl radical, the 1VPR isomers are the second 1-substituted propargyl species to have been observed abundantly from a hydrocarbon discharge, while no 3-substituted analogue has been positively identified. This is likely due to the greater resonance stabilization energy of the 1-substituted species, arising from concerted delocalization of the unpaired electron over the vinyl and propargyl moieties.
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