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

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Barton, Thomas
Lin, Jibing
Ijadi-Maghsoodi, Sina
Power, Martin
Zhang, Xianping
Ma, Zhongxin
Shimizu, Hideaki
Gordon, Mark
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Ames National Laboratory

Ames National Laboratory is a government-owned, contractor-operated national laboratory of the U.S. Department of Energy (DOE), operated by and located on the campus of Iowa State University in Ames, Iowa.

For more than 70 years, the Ames National Laboratory has successfully partnered with Iowa State University, and is unique among the 17 DOE laboratories in that it is physically located on the campus of a major research university. Many of the scientists and administrators at the Laboratory also hold faculty positions at the University and the Laboratory has access to both undergraduate and graduate student talent.

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Ames National LaboratoryChemistry

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.


Reprinted (adapted) with permission from Journal of the American Chemical Society 117 (1995): 11695, doi:10.1021/ja00152a010. Copyright 1995 American Chemical Society.

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Sun Jan 01 00:00:00 UTC 1995