¹⁷O-Dynamic NMR and DFT investigation of bis(acyloxy)iodoarenes.

Bis(acetoxy)iodobenzene and related acyloxy derivatives of hypervalent I(III) were studied by variable temperature solution-state ¹⁷O-NMR and DFT calculations. The ¹⁷O-NMR spectra reveal a dynamic process that interchanges the oxygen atoms of the acyloxy groups. For the first time, coalescence events could be detected for such compounds, allowing the determination of activation free energy data which are found to range between 44 and 47 kJ/mol.

Dynamic NMR of low-sensitivity fast-relaxing nuclei: (17)O NMR and DFT study of acetoxysilanes.

(17)O NMR is not routinely used for structure characterization, and kinetic studies of fluxional organic compounds are seldom undertaken because poor sensitivity and fast quadrupole relaxation are frequently regarded as intractable issues. This work shows how, nowadays, quantitative (17)O dynamic NMR studies on small organic molecules are feasible without enrichment being needed. It reports on acetoxysilanes, a class of fluxional compounds whose structure and dynamics were to be clarified.

On the fluxional behavior of Dess-Martin periodinane: a DFT and 17O NMR study.

The structure and dynamics of the Dess-Martin periodinane, a I(V) iodobenzene compound widely used in organic synthesis as a mild oxidant, were studied by a combined (17)O NMR and DFT calculations approach. The results show that a degenerate [1,3] sigmatropic shift of iodine between the two oxygen atoms of each of the three acetoxy groups occurs in solution. The energy barrier of this process depends on the position of the acetoxy group with respect to the iodoxolone ring and is much lower than the energy barrier observed for similar I(III) compounds.

Characterization of 2,5-diaryl-1,3,4-oxadiazolines by multinuclear magnetic resonance and density functional theory calculations. Investigation on a case of very remote Hammett correlation.

Two series of 2,5-diaryl-1,3,4-oxadiazolines have been studied by multinuclear magnetic resonance and density functional theory calculations. A full NMR spectroscopic characterization has been performed and excellent remote Hammett correlations (sigma(p) or sigma(p)+) have been found for para substitution in the two aryl rings through at least 11 bonds, notwithstanding the presence in the path of atoms that should act as insulators and a lack of correlation for some of the intermediate atoms. The computational investigation on the electronic delocalization, performed with the ACID (anisotropy of the induced current density) method, reveals indeed that electrons are delocalized in almost the entire molecule despite the presence of the insulators.

DFT and multinuclear magnetic resonance studies of diazenedicarboxylates and related compounds.

A number of diazenedicarboxylates have been studied by multinuclear magnetic resonance ((17)O, (15)N, (13)C) and compared with analogous fumaric, maleic, and phthalic diesters; the investigation of selected compounds of these classes was complemented by density functional theory (DFT) calculations using a polarizable continuum model (PCM) for the solvent, employing the PBE0 functional together with the 6-311G(d,p) basis set for geometry optimization, and the 6-311 + G(2d,p) basis set for calculating the NMR shielding using the gauge-including atomic orbital (GIAO) method. This combined approach provided important information about the preferred conformations in chloroform and their influence on the NMR parameters.

Solution structure of some lambda(3) Iodanes: an (17)O NMR and DFT study.

The structure of a series of I-O bonded bis(acyloxy)iodoarenes and benzoiodoxolones in chloroform solution has been investigated by 17O NMR spectroscopy and by density functional theory (DFT) calculations, employing the PBE0 functional together with the LANL2DZ basis set extended with polarization (d) and diffuse (p) functions. This combined approach allowed us to ascertain that, although these classes of lambda(3) iodanes maintain in chloroform solution their solid state "T-shaped" structure, a degenerate [1,3] sigmatropic shift of iodine between the two oxygens of the acyloxy groups occurs in solution. The energy barrier involved in this process differs in the two classes, thus causing significant differences in the 17O NMR spectra, at room temperature, of the two classes of compounds.

17O NMR spectra of alpha-diesters.

17O NMR spectra of title compounds were measured at natural abundance in acetonitrile solutions. Intercarbonyl dihedral angles have been estimated by molecular mechanics, which show invariance except in one case. Because of this invariance, contrary to other alpha-dicarbonyl compounds, a correlation between chemical shifts and dihedral intercarbonyl angles could not be developed.

Stable enols of amides ArNHC(OH)=C(CN)CO(2)R. E/Z enols, equilibria with the amides, solvent effects, and hydrogen bonding.

The structures of anilido cyano(fluoroalkoxycarbonyl)methanes ArNHCOCH(CN)CO(2)R, where R = CH(2)CF(3) or CH(CF(3))(2), Ar = p-XC(6)H(4), and X = MeO, Me, H, or Br, were investigated. In the solid state, all exist as the enols ArNHC(OH)=C(CN)CO(2)R 7 (R = CH(2)CF(3)) and 9 (R = CH(CF(3))(2)) with cis arrangement of the hydrogen-bonded ROC=O.HO moiety and a long C1=C2 bond.

Cyclobutene-1,2-diones. A Theoretical and Spectroscopic Study.

The properties of substituted cyclobutene-1,2-diones 1 are examined by the use of (17)O NMR spectroscopy and theoretical calculations and compared to those of cyclopropenones 2 and other models. Cyclobutene-1,2-diones have less negative charge per oxygen compared to cyclopropenones, and electron donation by substituents enhances the negative charge on oxygen. Calculated (17)O chemical shifts reproduce the measured trends.