Synthesis of precursors of a highly pyramidalized alkene and ab initio calculations on methylenecyclopropane, cyclopropene, and 1,3-diradicals

ResearchWorks/Manakin Repository

Search ResearchWorks


Advanced Search

Browse

My Account

Statistics

Related Information

Synthesis of precursors of a highly pyramidalized alkene and ab initio calculations on methylenecyclopropane, cyclopropene, and 1,3-diradicals

Show simple item record

dc.contributor.author Johnson, William T. G en_US
dc.date.accessioned 2009-10-07T15:20:32Z
dc.date.available 2009-10-07T15:20:32Z
dc.date.issued 1999 en_US
dc.identifier.other b43896200 en_US
dc.identifier.other 43973579 en_US
dc.identifier.other Thesis 48641 en_US
dc.identifier.uri http://hdl.handle.net/1773/11586
dc.description Thesis (Ph. D.)--University of Washington, 1999 en_US
dc.description.abstract The synthesis of precursors for the highly pyramidalized olefin 3,7-dimethyltricyclo[3.3.0.03,7]octane are described within. Three computational projects are also contained in this thesis. In the first, the increase in strain energy that results from placing a trigonal center in a cyclopropane ring is shown to be due to the loss of a stabilizing cyclopropyl C-H bond, not an increase in angle strain. In the second, the singlet state of a derivative of the trimethylene diradical is shown to be stabilized to such an extent relative to the closed cyclopropane as to make the two isomers nearly isoenergetic. The barrier for closure of the trimethylene derivative via enforced disrotation is also shown to be quite high, owing to the substitution at C-2 of the diradical with silyl groups. In the third, previous experimental results are reinterpreted showing that spiropentane opens via conrotation, in agreement with qualitative molecular orbital theory. A long range interaction between a terminal methyl group in pentane-2,4-diyl and the more distant radical center is described. The interaction is found to be stabilizing when C-3 is substituted with donors, and destabilizing when C-3 is substituted with acceptors. en_US
dc.format.extent v, 89 p. en_US
dc.language.iso en_US en_US
dc.rights.uri en_US
dc.subject.other Theses--Chemistry en_US
dc.title Synthesis of precursors of a highly pyramidalized alkene and ab initio calculations on methylenecyclopropane, cyclopropene, and 1,3-diradicals en_US
dc.type Thesis en_US


Files in this item

Files Size Format View
9944133.pdf 3.430Mb PDF View/Open

This item appears in the following Collection(s)

Show simple item record