title: A comparative ab initio study of intramolecular proton transfer in model alpha-hydroxyalkoxides.
abstract: A comparative ab initio study was performed on the intramolecular proton-transfer reaction that occurs in alpha-hydroxyethanoxy, alpha-hydroxyphenoxide, and alpha-hydroxyethenoxy anions. The intramolecular proton transfer occurs in a five-member atom arrangement, between two oxygen atoms separated by a carbon-carbon bond. The chosen systems serve as models for alpha-hydroxyalkoxide molecules where the carbon-carbon bond varies from a single bond (the glycolate anion or alpha-hydroxyethanoxide anion) to a part of an aromatic ring (the alpha-hydroxyphenoxide anion), and finally to a double bond (the alpha-hydroxyethenoxide anion). Particular attention was given to the evolution along the intrinsic reaction coordinate of such properties as energies, relevant structural parameters, Mulliken charges, dipole moments, and 1H-NMR chemical shifts to reveal the similarities and differences for the proton transfer in the model systems.
authors.affiliation: Department of Chemistry, DePaul University, Chicago, Illinois 60614, USA. rparral@depaul.edu
authors.forename: Rubén D
authors.initials: RD
authors.lastname: Parra
authors.forename: Igor
authors.initials: I
authors.lastname: Dukarevich
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000838:Anions / Q000737:chemistry*; D004987:Ethers / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D011522:Protons
chemical_list: D000438:Alcohols; D000838:Anions; D004987:Ethers; D011522:Protons