Preference for an ion-neutral complex-mediated pathway over a five-membered-ring H shift in the isomerization of CH3O+HCH2CH2·to CH3CH2CH2OH+·by Ab initio theory
✍ Scribed by Charles E. Hudson; David J. McAdoo; Lawrence L. Griffin
- Publisher
- Elsevier Science
- Year
- 1995
- Tongue
- English
- Weight
- 999 KB
- Volume
- 6
- Category
- Article
- ISSN
- 1044-0305
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✦ Synopsis
Ab initio theory is used tO explore whether the path from CH3OH+CH2CH2 (1) to CH3CHRCH2OH +" (5) goes by way of a conventional 1,4-H shift to form -CH2OH÷CH2CH3 (2), or via the ion-neutral complex-mediated H transfer [C,I-I3OHCH2=CH2] +" (3) [CH3CH 2 CH2OH + ] (4)i Five levels of theory all place the highest energy point in the complex-mediated reaction 3 ~ 4 slightly below that for the 1,4-H shift 1 --* 2, but both routes appear energetically feasible near the threshold for the dissociation of 1 to CHBCH 2 + CH2~OH +. Thus, 1 may take both paths to 5. It is concluded that when both a conventional and a complex-mediated pathway Seem plausible in a given system, the latter should be considered to be as likely as the former, Ab initio descriptions of other species involved in the isomerization of 1 to 2 also are presented.