Theoretical evidence for the nucleophilic addition of sulfur dioxide to 1,2-bridged chloronium and bromonium ions.

The nucleophilic addition of SO2, SO2ClF, and SO2F2 to carbenium ions and the nucleophilic addition of SO2 to 1,2-bridged halonium ions are theoretically investigated by using B3LYP/6-311+G(d,p). On the basis of geometric changes in ion-solvent complexes compared to isolated molecules, the theoretical data for the addition of solvent to carbenium ions uniformly agree with experiments by Olah and Donovan. The relative reactivity of carbenium ions (methyl > ethyl > iso-propyl > tert-butyl) follows the familiar trend based on electron demand at the carbenium center.

Evidence for beta-chlorocarbenium and beta-bromocarbenium ions.

Isotopic perturbation of degenerate equilibrium is used to determine whether tetramethylethylenechloronium and tetramethylethylenebromonium ions are closed 1,2-bridged structures or rapid equilibria of open beta-halocarbenium ions. The observed 13C NMR isotope shifts are consistent with a combination of large equilibrium shifts and small upfield intrinsic shifts. The presence of equilibrium shifts in both halonium ions indicates that these ions are not closed 1,2-bridged structures.

Theoretical investigation of lone pair inversions, ring openings, and hydride shifts in O-methylated epoxides.

Mechanisms associated with the isomerization of the O-methylethylene oxonium ion and its tetramethyl-substituted analogue have been explored using correlated electronic structure calculations. The minima and transition states associated with inversion at the oxygen atom, as well as those associated with opening of the epoxide ring, have been characterized. The calculated barrier to inversion at the oxygen atom for the O-methylethylene oxonium ion, 15.

Stereochemistry of beta-deuterium isotope effects on amine basicity.

Secondary beta-deuterium isotope effects on amine basicities are measured using a remarkably precise NMR titration method. Deuteration is found to increase the basicity of methylamine, dimethylamine, benzylamine, N,N-dimethylaniline, 2-methyl-2-azanorbornane, and pyrrolizidine. The increase in dimethylamine arises entirely from enthalpy, contrary to a previous report.

Beta-deuterium isotope effects on amine basicity, "inductive" and stereochemical.

Secondary beta deuterium isotope effects on acidity constants of ammonium ions are measured using a remarkably precise NMR titration method. Deuteration is found to increase the basicity of methylamine, dimethylamine, benzylamine, and N,N-dimethylaniline. The effect is attributed to a lowered zero-point energy of a CH bond adjacent to an amine nitrogen.

Characterization of endoperoxide and hydroperoxide intermediates in the reaction of pyridoxine with singlet oxygen.

The photosensitized oxidation of vitamin B6, pyridoxine, is investigated by product and kinetic analysis. Singlet oxygen quenching rates, measured by time-resolved laser flash generation of singlet oxygen followed by monitoring singlet oxygen phosphorescence decay, confirm previous observations that pyridoxine is a moderate quencher. The quenching rate for 3-methoxypyridine is 100 times slower than that for 3-hydroxypyridine, indicating the hydroxy moiety is required for efficient quenching.

Symmetry of O-H-O and N-H-N hydrogen bonds in 6-hydroxy-2-formylfulvene and 6-aminofulvene-2-aldimines.

The symmetry of the hydrogen bonds in 6-hydroxy-2-formylfulvene and two N,N'-diaryl-6-aminofulvene-2-aldimines is probed by the NMR technique of isotopic perturbation. Observed deuterium-induced 13C NMR isotope shifts at several positions can be attributed to a combination of an intrinsic shift and the perturbation of a tautomeric equilibrium. The most dramatic are at the aldehydic or aldiminic carbon signals, where the observed isotope shift for the unlabeled carbon is +376 or +223 ppb.