An Ab Initio study of the bicyclobutyl radical: An anti-W long-range coupled system

King, Frederick W.; Schlegel, H. Bernhard

doi:10.1016/0022-2364(76)90313-9

Cited by 3 publications

(1 citation statement)

References 10 publications

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“…18 Due to their high reactivity, strained C 4 H 5 isomers ͑7͒-͑10͒ could only be identified in solid matrices at 77 K via ESR spectroscopy after irradiating distinct hydrocarbon precursors with Co 60 ␥-rays, but thermodynamical data are missing. [19][20][21][22][23][24] Finally, a methylallyl isomer which even resisted matrix trapping was stabilized by metal atoms as a 3 -diosmiumate complex ͑11͒. 25 The work reported here is part of an ongoing project to elucidate the potential energy surfaces and chemical reaction dynamics of carbon atoms in their C( 3 P j ) electronic ground state with unsaturated hydrocarbons under single collision conditions.…”

Section: ͑9͒mentioning

confidence: 99%

Crossed-beam reaction of carbon atoms with hydrocarbon molecules. IV. Chemical dynamics of methylpropargyl radical formation, C4H5, from reaction of C(3Pj) with propylene, C3H6 (X 1A)

Kaiser

Stranges

Bevsek

et al. 1997

The Journal of Chemical Physics

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The reaction between ground state carbon atoms and propylene, C3H6, was studied at average collision energies of 23.3 and 45.0 kJ mol−1 using the crossed molecular beam technique. Product angular distributions and time-of-flight spectra of C4H5 at m/e=53 were recorded. Forward-convolution fitting of the data yields a maximum energy release as well as angular distributions consistent with the formation of methylpropargyl radicals. Reaction dynamics inferred from the experimental results suggest that the reaction proceeds on the lowest A3 surface via an initial addition of the carbon atom to the π-orbital to form a triplet methylcyclopropylidene collision complex followed by ring opening to triplet 1,2-butadiene. Within 0.3–0.6 ps, 1,2-butadiene decomposes through carbon–hydrogen bond rupture to atomic hydrogen and methylpropargyl radicals. The explicit identification of C4H5 under single collision conditions represents a further example of a carbon–hydrogen exchange in reactions of ground state carbon with unsaturated hydrocarbons. This versatile machine represents an alternative pathway to build up unsaturated hydrocarbon chains in combustion processes, chemical vapor deposition, and in the interstellar medium.

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