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A combined crossed beam and ab initio investigation of the gas phase reaction of dicarbon molecules (C2; X1Σg(+)/a3Πu) with propene (C3H6; X1A'): identification of the resonantly stabilized free radicals 1- and 3-vinylpropargyl

, : A combined crossed beam and ab initio investigation of the gas phase reaction of dicarbon molecules (C2; X1Σg(+)/a3Πu) with propene (C3H6; X1A'): identification of the resonantly stabilized free radicals 1- and 3-vinylpropargyl. Journal of Physical Chemistry. A 117(46): 11783-11793

The crossed molecular beam reactions of dicarbon, C2(X(1)Σg(+), a(3)Πu), with propene (C3H6; X(1)A') and with the partially deuterated D3 counterparts (CD3CHCH2, CH3CDCD2) were conducted at collision energies of about 21 kJ mol(-1) under single collision conditions. The experimental data were combined with ab initio and statistical (RRKM) calculations to reveal the underlying reaction mechanisms. Both on the singlet and triplet surfaces, the reactions involve indirect scattering dynamics and are initiated by the addition of the dicarbon reactant to the carbon-carbon double bond of propene. These initial addition complexes rearrange via multiple isomerization steps leading ultimately via atomic hydrogen elimination from the former methyl and vinyl groups to the formation of 1-vinylpropargyl and 3-vinylpropargyl. Both triplet and singlet methylbutatriene species were identified as important reaction intermediates. On the singlet surface, the unimolecular decomposition of the reaction intermediates was found to be barrier-less, whereas on the triplet surface, tight exit transition states were involved. In combustion flames, both radicals can undergo a hydrogen-atom assisted isomerization leading ultimately to the thermodynamically most stable cyclopentadienyl isomer. Alternatively, in a third body process, a subsequent reaction of 1-vinylpropargyl or 3-vinylpropargyl radicals with the propargyl radical might yield to the formation of styrene (C6H5C2H3) in an entrance barrier-less reaction under combustion-like conditions. This presents a strong alternative to the formation of styrene via the reaction of phenyl radicals with ethylene, which is affiliated with an entrance barrier of about 10 kJ mol(-1).


PMID: 23682723

DOI: 10.1021/jp402700j

Other references

Avedillo, M., 1976: Economic evaluation of agricultural research: foundations for an eclectic approach. A framework and methodology are established whereby the applied value of agricultural research may be assessed. Three case studies from Latin America are then analyzed using the methodology.

Hansson, M.G., 2011: The need to downregulate: a minimal ethical framework for biobank research. There are currently multiple international bodies suggesting legal and ethical frameworks for regulating international biobank research. One will for obvious reasons find inconsistencies in terminology and differences in procedures suggested for b...

von Uexküll, T., 1986: History of German psychosomatic medicine--philosophical and historical roots. Psychotherapie, Psychosomatik, Medizinische Psychologie 36(1): 18-24

Troll, M.; Schuhmann, H., 1984: Tax primer for agriculture and forestry. The book presents a comprehensive treatment of W. German forestry taxes, with special reference to income tax.

Anonymous., 2001: In memory of Maksim Fedorovich Veklich. Heolohichnyi Zhurnal, 2: 127

Dietze, Ringo., 2004: Contributions to the beetle fauna of Sachsen-Anhalt 3 current records of Anthicidae in the south of Saxony-Anhalt Col, Anthicidae Beitraege zur Kaeferfauna Sachsen-Anhalts 3 Aktuelle Nachweise von Anthiciden im Sueden Sachsen-Anhalts Col, Anthicidae. Entomologische Nachrichten und Berichte, 481: 55-56

von Elm, E.; Altman, D.G.; Egger, M.; Pocock, S.J.; Gøtzsche, P.C.; Vandenbroucke, J.P., 2007: Strengthening the Reporting of Observational Studies in Epidemiology (STROBE) statement: guidelines for reporting observational studies. Bmj 335(7624): 806-808

Iizuka, H.; Takahashi, H., 1993: Psoriasis, involucrin, and protein kinase C. International Journal of Dermatology 32(5): 333-338

Feder, J.L.; Egan, S.P.; Nosil, P., 2012: The genomics of speciation-with-gene-flow. The emerging field of speciation genomics is advancing our understanding of the evolution of reproductive isolation from the individual gene to a whole-genome perspective. In this new view it is important to understand the conditions under which &...

Glebezdin V.S.; Babich V.V., 1974: Study of coccidial fauna from the red tailed jird meriones erythrourus in the turkmen ssr ussr. Izvestiya Akademii Nauk Turkmenskoi SSR Seriya Biologicheskikh Nauk (2): 84-87