Article ID Journal Published Year Pages File Type
5416905 Journal of Molecular Structure: THEOCHEM 2010 7 Pages PDF
Abstract
Conceptual density functional theory based reactivity descriptors are used to study nucleophilic reactivity of silyl enol ethers and ketene silyl acetals having substituents of both electron releasing and electron withdrawing nature at various key positions of the molecules. While intramolecular reactivity towards electrophilic attack is studied on the basis of local softness (sk-) and local nucleophilicity index (Nk), intermolecular reactivity is assessed using group softness (sg-) and group nucleophilicity (Ng). Ionization potential, inner sphere reorganization energy and structural changes associated with single electron-transfer oxidation for the selected trimethylsilyl enolates have been evaluated. Role of β-methyl substituents are found to be crucial for both nucleophilic reactivity and single electron-transfer oxidation of these systems.
Related Topics
Physical Sciences and Engineering Chemistry Physical and Theoretical Chemistry
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