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Schuster, Gary B. Hartsough, David Scott 2011-05-07T12:07:27Z 2011-05-07T12:07:27Z 10000-01-01 1991 The (4+2) cycloaddition of an electron-rich diene to an electron-rich dienophile may be catalyzed by irradiation of a cyanoarene. This reaction is shown to proceed through an intermediate ternary excited state complex (triplex) and is therefore called the triplex Diels-Alder reaction. Evidence is presented demonstrating the ability of this process to catalyze the additions of acyclic dienophiles to a cyclic diene. Furthermore, this reaction is found to occur with a high degree of syn stereospecificity. Local density functional theory as implemented in the program DMol is examined as a method for the evaluation of interactions between $\pi$-electron containing molecules. For the evalution of interactions between acetylene and various substituted acetylenes DMol is found to correlate quite well with MP2 calculations using a 6-31G* basis set. DMol is then used to evaluate the interactions between larger $\pi$-electron containing molecules (benzene and substituted benzenes). It is found for eclipsed binary aromatic complexes that a positive correlation exists between the energetic bias favoring the edge-face over the face-face form of the complex and the electron richness of one of the members of the complex. Conversely, it is found that the presence of an electron deficient member lowers the energetic bias favoring the edge-face form of the complex. Additionally, there is a large driving force for sliding the rings apart from the eclipsed geometry in face-face complexes containing an electron rich member. In complexes containing an electron deficient member this driving force is much less. These observations can best be understood on the basis of the electrostatic interactions between the $\pi$-electron systems. Made available in DSpace on 2011-05-07T12:07:27Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210829.pdf: 5430366 bytes, checksum: 1e26da979e2bf2864876172ff0e2a83a (MD5) Previous issue date: 1991 Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:36:56Z Item is restricted indefinitely. Restriction data tranferred 2014-07-01T11:15:05-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission ETDs are only available to UIUC Users without author permission U of I Only AAI9210829 (UMI)AAI9210829 http://hdl.handle.net/2142/19435 eng Copyright 1991 Hartsough, David Scott Chemistry, Organic Triplex Diels-Alder reactions of beta-methylstyrenes. Density functional investigation of pion-pion interactions text Chemistry, Organic Chemistry, Organic University of Illinois at Urbana-Champaign Dissertation Ph.D.