title: B values as a sensitive measure of steric effects.
abstract: Someone who says "A" should be prepared to also say "B": In contrast to cyclohexane model-based A values, biphenyl model-derived B values are powerful tools to quantify steric repulsion in and conformational behavior of ortho-substituted aromatic compounds.Torsional barriers of 15 ortho-substituted biphenyls have been determined computationally using the B3LYP density functional and experimentally by variable-temperature ("dynamic") nuclear magnetic resonance. Taking advantage of the 3'-isopropyldimethylsilyl group as a novel and superior diastereotopicity probe and tracking coalescence temperatures down to -173 degrees C (100 K), activation energies of aryl-aryl rotation as small as 5 kcal mol(-1) can be assessed. The 2-X/2'-H repulsion increments thus derived are powerful parameters for rationalizing and predicting the conformational behavior of aromatic compounds carrying ortho substituents.
authors.affiliation: Chemistry Department, University, Via Elce di Sotto 10 06100 Perugia, Italy. ruzzchor@unipg.it
authors.forename: Renzo
authors.initials: R
authors.lastname: Ruzziconi
authors.forename: Sara
authors.initials: S
authors.lastname: Spizzichino
authors.forename: Lodovico
authors.initials: L
authors.lastname: Lunazzi
authors.forename: Andrea
authors.initials: A
authors.lastname: Mazzanti
authors.forename: Manfred
authors.initials: M
authors.lastname: Schlosser