title: Determination of the conformation of 2-hydroxy- and 2-aminobenzoic acid dimers using 13C NMR and density functional theory/natural bond order analysis: the central importance of the carboxylic acid carbon.
abstract: The 13C chemical shift for the carboxylic acid carbon provides a powerful diagnostic probe to determine the preferred isomeric dimer structures of benzoic acid derivatives undergoing intra- and intermolecular H-bonding in the gas, solution and crystalline phases. We have employed hybrid density functional calculations and natural bond orbital analysis to elucidate the electronic origins of the observed 13C shieldings and their relationship to isomeric stability. We find that delocalizing interactions from the carbonyl oxygen lone pairs (nO) into vicinal carbon-oxygen and carbon-carbon antibonds (sigmaCO*,sigmaCC*) make critical contributions to the 13C shieldings, and these nO --> sigmaCO*, nO --> sigmaCC* interactions are in turn sensitive to the intramolecular interactions that dictate dimer structure and stability. The carboxyl carbon atom can thus serve as a useful detector of subtle structural and conformational features in this pharmacologically important class of carboxylic acid interactions.
authors.affiliation: School of Pharmacy and the Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53705, USA. rrburnette@pharmacy.wisc.edu
authors.forename: Ronald R
authors.initials: RR
authors.lastname: Burnette
authors.forename: Frank
authors.initials: F
authors.lastname: Weinhold
mesh_terms: D062365:Aminobenzoates / Q000737:chemistry*; D002236:Carbohydrate Conformation; D002244:Carbon / Q000737:chemistry*; D002247:Carbon Isotopes; D019281:Dimerization; D006860:Hydrogen Bonding; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory
chemical_list: D062365:Aminobenzoates; D002247:Carbon Isotopes; D002244:Carbon