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Ab initio studies of pericyclic reactions involving phosphorus substituted alkenes and alkynes

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dc.contributor.advisor Bachrach, Steven M., 1959- en_US Magdalinos, Peter en_US 2016-01-11T17:13:14Z 2016-01-11T17:13:14Z 1997
dc.description Includes bibliographical references (pages [46]-48) en_US
dc.description.abstract The Diels-Alder Reaction between 1,3,5-triphosphabenzene and phosphaacetylene, forming tetraphosphabarrelene, was examined. This reaction was then compared to its carbon analogue (benzene + acetylene). The phosphorus reaction gave a smaller activation energy than the carbon system, as well as producing a higher degree of exothermicity. These results are consistent with the previous work done on phosphorus substituted systems. All structures were optimized to the MP4/6-31G*//MP2/6-31G* level. Transition states, as well as ground states, were verified by analytical frequency calculations. Topological electron density analysis was performed on all species, and showed that both reactions are synchronous and concerted. Secondly, the [2+2] cycloaddition (self-addition) of 1H, 3Himinomethylidene phosphine was studied. Resulting products were a variety of 1,2- and 1,3- diphosphetane isomers. Our investigation reveals that formation of the 1,2-diphosphetanes proceeds in a single step, while the 1,3-diphosphetane is formed via a two step mechanism. Formation of the 1,3- product is kinetically favored, and is usually the observed product. The 1,2- product is thermodynamically favored, but is only observed under certain conditions. en_US
dc.format.extent iv, 48 pages en_US
dc.language.iso eng en_US
dc.publisher Northern Illinois University en_US
dc.rights NIU theses are protected by copyright. They may be viewed from Huskie Commons for any purpose, but reproduction or distribution in any format is prohibited without the written permission of the authors. en_US
dc.subject.lcsh Organophosphorus compounds en_US
dc.subject.lcsh Alkenes en_US
dc.subject.lcsh Chemistry, Physical organic en_US
dc.subject.lcsh Alkynes en_US
dc.title Ab initio studies of pericyclic reactions involving phosphorus substituted alkenes and alkynes en_US
dc.type.genre Dissertation/Thesis en_US
dc.type Text en_US
dc.contributor.department Department of Chemistry en_US M.S. (Master of Science) en_US

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