Gas-phase reactions of organic radicals and diradicals with ions |
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Authors: | Zhang Xu Bierbaum Veronica M Ellison G Barney Kato Shuji |
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Institution: | Department of Chemistry and Biochemistry, University of Colorado, Boulder, 80309-0215, USA. Xu.Zhang@colorado.edu |
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Abstract: | Reactions of polyatomic organic radicals with gas phase ions have been studied at thermal energy using a flowing afterglow-selected ion flow tube (FA-SIFT) instrument. A supersonic pyrolysis nozzle produces allyl radical (CH2CHCH2) and ortho-benzyne diradical (o-C6H4) for reaction with ions. We have observed: CH2CHCH2 + H3O+ --> C3H6+ + H2O], CH2CHCH2 + HO- --> no ion products], o-C6H4 + H3O+ --> C6H5+ + H2O], and o-C6H4 + HO- --> C6H3- + H2O]. The proton transfer reactions with H3O+ occur at nearly every collision (kII approximately with 10(-9) cm3 s(-1)). The exothermic proton abstraction for o-C6H4 + HO- is unexpectedly slow (kII approximately with 10(-10) cm3 s(-1)). This has been rationalized by competing associative detachment: o-C6H4 + HO- --> C6H5O + e-. The allyl + HO- reaction proceeds presumably via similar detachment pathways. |
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