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Full-Text Articles in Computational Chemistry
Additivity Of Diene Substituent Gibbs Free Energy Contributions For Diels–Alder Reactions Between Me2c=Cme2 And Substituted Cyclopentadienes, Thomas M. Gilbert, Austin S. Flemming, Brendan C. Dutmer
Additivity Of Diene Substituent Gibbs Free Energy Contributions For Diels–Alder Reactions Between Me2c=Cme2 And Substituted Cyclopentadienes, Thomas M. Gilbert, Austin S. Flemming, Brendan C. Dutmer
Faculty Peer-Reviewed Publications
Systematic computational studies of pericyclic Diels–Alder reactions between (H3C)2C═C(CH3)2, 1, and all permutations of substituted cyclopentadienes c-C5R1R2R3R4R5aR5b (R = H, CH3, CF3, F) allowed isolation of substitutional effects on Gibbs free energy barrier heights and reaction Gibbs free energies. “Average Substitution Gibbs Free Energy Correction” ΔGASC#‡/ΔGASC# values for each substituent in each position appeared to be additive. Substituent effects on barriers showed interesting contrasts. Methyl substitution at positions 5a and 5b increased barriers significantly, while substitution at all other positions had essentially no impact. In contrast, fluoro substitution at positions 5a and 5b lowered barriers more than substitution at other …
Computational Studies Of The Effects Of Substitutions On Silatranes And Ring Strain Energies, As Well As Determination Of Aromaticity And Complexation In Polypnictogen Analogues Of The Cyclooctatetraenyl Dianion, Alexander Stuart Pixler
Computational Studies Of The Effects Of Substitutions On Silatranes And Ring Strain Energies, As Well As Determination Of Aromaticity And Complexation In Polypnictogen Analogues Of The Cyclooctatetraenyl Dianion, Alexander Stuart Pixler
Graduate Research Theses & Dissertations
The work in this dissertation computationally examines four areas involving variations on archetype molecules and how they affect reactivity and physical properties. Studies in Chapters 2 and 3 assess substituent effects on cyclic systems, while those in Chapters 4 and 5 explore both partial and complete substitution of ring component atoms as well as the chemical implications of the substitution.The effect of substituents on molecular reactivity is a critical concept that affects every branch of chemistry. Previous work within our group showed that 1-hydridosilatrane was an effective and selective reducing agent for a variety of compounds. Fully 3,3,7,7,10,10-substituted silatranes have …
Structural Analysis Of Polar Aggregates And Inter-Ionic Distances In Room Temperature Ionic Liquids, Emily Elizabeth Dalbey
Structural Analysis Of Polar Aggregates And Inter-Ionic Distances In Room Temperature Ionic Liquids, Emily Elizabeth Dalbey
Graduate Research Theses & Dissertations
Ionic liquids have a wide variety of applications in chemistry due to their unique properties such as low flammability, low volatility, and high thermal and chemical stability. These properties make them great solvents, electrolytes for lithium-ion batteries, and more. Ionic liquids are salts whose components are mis-matched in size and shape leading to low melting points. To design an ionic liquid with a desired property it is key to first understand their structure. Lineshape analysis of the charge alternation peak from the experimentally measured or computationally calculated X-ray scattering data can give information about the size of the polar aggregates …