Thermally-Induced 1,2-Shifts To Convert Olefins to Carbenes: Does Silicon Do It? If So, Why Not Carbon?

dc.contributor.author Barton, Thomas
dc.contributor.author Lin, Jibing
dc.contributor.author Ijadi-Maghsoodi, Sina
dc.contributor.author Gordon, Mark
dc.contributor.author Power, Martin
dc.contributor.author Zhang, Xianping
dc.contributor.author Ma, Zhongxin
dc.contributor.author Shimizu, Hideaki
dc.contributor.author Gordon, Mark
dc.contributor.department Ames Laboratory
dc.contributor.department Chemistry
dc.date 2018-02-17T07:44:25.000
dc.date.accessioned 2020-06-30T01:19:07Z
dc.date.available 2020-06-30T01:19:07Z
dc.date.copyright Sun Jan 01 00:00:00 UTC 1995
dc.date.issued 1995-11-01
dc.description.abstract <p>Thermal isomerization of olefins to carbenes via a 1,2-silyl shift was examined by both experiment and theory. No evidence of this rearrangement was found for acyclic vinylsilanes, nor could electronic assistance by silicon be identified in cis, trans isomerizations. Serendipitous synthesis of a 2,4-dimethylene-1,3-disilacyclobutane allowed a kinetic examination of its gas-phase, thermal ring expansion to a 2-methylene-1,3-disilacyclopentene. The Arrhenius parameters (log A = 12.48, Eact = 54.09 kcallmol) are the first to be reported for an olefin-to-carbene rearrangement. The analogous all-carbon system failed to ring expand. Ab initio calculations revealed that this was opposite to any predictions which would be made from ring strain considerations. Calculations showed that for silyl migration the transition state was late and was actually the carbene, while for carbon migration the TS was early and considerably higher in energy than the resulting carbene. The 2-methylene-1-silacyclobutane rearrangement (ref 5) was reexamined to find that reversible ring opening to a 1,4-diradical occurred at temperatures below those required to ring expand via a carbene TS.</p>
dc.description.comments <p>Reprinted (adapted) with permission from <em>Journal of the American Chemical Society </em>117 (1995): 11695, doi:<a href="http://dx.doi.org/10.1021/ja00152a010" target="_blank">10.1021/ja00152a010</a>. Copyright 1995 American Chemical Society.</p>
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dc.identifier archive/lib.dr.iastate.edu/chem_pubs/299/
dc.identifier.articleid 1289
dc.identifier.contextkey 7920504
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath chem_pubs/299
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/14744
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/299/0-L_1995_Gordon_ThermallyInduced.pdf|||Fri Jan 14 23:15:56 UTC 2022
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/299/1995_Gordon_ThermallyInduced.pdf|||Fri Jan 14 23:15:57 UTC 2022
dc.source.uri 10.1021/ja00152a010
dc.subject.disciplines Chemistry
dc.title Thermally-Induced 1,2-Shifts To Convert Olefins to Carbenes: Does Silicon Do It? If So, Why Not Carbon?
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication 1a5927c0-5a5f-440e-86e0-9da8dc6afda0
relation.isOrgUnitOfPublication 25913818-6714-4be5-89a6-f70c8facdf7e
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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