title: Investigation of the dynamic stereochemistry of dimesityl-2,4,6-trimethoxyphenylmethane by complete lineshape analysis and 2D EXSY NMR spectroscopy.
abstract: The static and dynamic stereochemistry of dimesityl-2,4,6-trimethoxyphenylmethane in solution was investigated by lineshape analysis of 1D NMR spectra and cross-peak amplitude processing in 2D EXSY spectra, recorded at variable temperatures. Previous studies on this propeller-shaped chiral compound show that the stereomer threshold interconversion is associated with helicity reversal and occurs through [1,2]- and [1,3]-two ring flips of one mesityl and the 2,4,6-trimethoxyphenyl rings. In the present study, the experimental rate constants of the [1,2]- and [1,3]-two ring flips, which are identical, were determined at various temperatures by combining quantitative 2D EXSY spectra processing and complete lineshape analysis (CLSA) of 1D NMR spectra. The latter were subjected to reference deconvolution and linear prediction in order to eliminate the lineshape distortions due to magnetic field inhomogeneity. The activation parameters of these ring flips were determined by an Eyring equation analysis of the temperature dependence of the rate constant. The experimentally determined activation enthalpy and entropy for the two-ring flips, and those obtained from theoretical ab initio calculations at different levels of theory and basis sets, were found to be in good agreement.
authors.affiliation: NMR Laboratory, Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences; Acad. G. Bontchev Str., Bl.9, 1113 Sofia, Bulgaria. psd@orgchm.bas.bg
authors.forename: Pavletta
authors.initials: P
authors.lastname: Denkova
authors.forename: Nikolay
authors.initials: N
authors.lastname: Vassilev
authors.forename: Luk
authors.initials: L
authors.lastname: Van Lokeren
authors.forename: Rudolph
authors.initials: R
authors.lastname: Willem
mesh_terms: D001555:Benzene Derivatives / Q000032:analysis*; D003198:Computer Simulation; D009682:Magnetic Resonance Spectroscopy / Q000379:methods* / Q000592:standards; D008956:Models, Chemical; D008968:Molecular Conformation; D011789:Quantum Theory; D012015:Reference Standards; D013237:Stereoisomerism; D013696:Temperature
chemical_list: D001555:Benzene Derivatives; C528028:dimesityl-2,4,6-trimethoxyphenylmethane