Isomerization of Silylallene

dc.contributor.author Shimizu, Hideaki
dc.contributor.author Gordon, Mark
dc.contributor.author Gordon, Mark
dc.contributor.department Chemistry
dc.date 2018-02-17T07:44:32.000
dc.date.accessioned 2020-06-30T01:19:06Z
dc.date.available 2020-06-30T01:19:06Z
dc.date.copyright Sun Jan 01 00:00:00 UTC 1995
dc.date.issued 1995-08-01
dc.description.abstract <p>The isomerization of silylallene to seven of its isomers has been studied using ab initio molecular orbital theory. The energetics were obtained using quadratically convergent configuration interaction (QCISD(T)) with the 6-311G(d,p) basis set, at geometries optimized by second-order perturbation theory (MP2) with the 6-31G(d) basis set. Test calculations using multiconfiguration wave functions show that the configurational mixing is small; therefore, the single-configuration-based methods are reliable. In comparison to the isomerization of the parent allene, the silyl group was found to migrate more easily than the hydrogen. In particular, the 1,3-migration that converts silylallene to silylpropyne has barriers of 55.8 and 52.9 kcal mol-1 for the forward and backward reactions, respectively. These are roughly half of the 1,3-hydrogen migration barrier in allene.</p>
dc.description.comments <p>Reprinted (adapted) with permission from <em>Organometallics</em> 14 (1005): 3827, doi:<a href="http://dx.doi.org/10.1021/om00008a033" target="_blank">10.1021/om00008a033</a>. Copyright 1995 American Chemical Society.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/chem_pubs/298/
dc.identifier.articleid 1290
dc.identifier.contextkey 7920542
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath chem_pubs/298
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/14743
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/298/0-L_1995_Gordon_IsomerizationSilylallene.pdf|||Fri Jan 14 23:15:43 UTC 2022
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/298/1995_Gordon_IsomerizationSilylallene.pdf|||Fri Jan 14 23:15:44 UTC 2022
dc.source.uri 10.1021/om00008a033
dc.subject.disciplines Chemistry
dc.title Isomerization of Silylallene
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication 1a5927c0-5a5f-440e-86e0-9da8dc6afda0
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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