Photoelectron spectra and dihedral angles of disulfides

Gas‐Phase Generation, Structure, Spectroscopy, and Quantum Chemical Calculations of Fluorocarbonylsulfur Thiocyanate, FC(O)SSCN

“…The energy difference Δ E between the first two bands in FC(O)SSCN is 0.50 eV, which is similar to that of FC(O)SSCH 3 [Δ E = 0.3 eV, δ CSSC = 83.5(1.5)°] 2. As pointed out by Baker et al,51,52 for disulfides, peroxides, and diselenides, the first two bands in the photoelectron spectra correspond to the symmetric and antisymmetric linear combinations of the S 3p atomic orbitals. In general, it is expected that as the dihedral angle δ CSSC deviates from 90° the energy separation Δ E between the pπ‐ and pπ*‐orbitals will increase, i.e.…”

Two Novel Species, (Methoxycarbonyl)sulfenyl Thiocyanate and (Methoxycarbonyl)sulfenyl Selenocyanate: Spectroscopic Characterization by Photoelectron Spectroscopy and Quantum Chemical Investigation

“…As pointed out by Baker et al,34 for disulfides, peroxides, and diselenides, the first two bands in the photoelectron spectra correspond to the symmetric and antisymmetric linear combinations of the outermost p ‐atomic orbitals. The first two peaks in the photoelectron spectrum of CH 3 OC(O)SSCN are centered at 10.19 and 10.60 eV.…”

Nitrogen-15 nuclear magnetic resonance spectroscopy. Natural-abundance nitrogen-15 chemical shifts of ring-methylated N,N-dimethylanilines. Effect of inhibition of conjugation

“…The decrease in has been correlated with the torsional angle about the Ci-N bond, with values (55 and 69°for lb and 2b, respectively) in good agreement with those estimated from UV data6b and from pKa values of substituted benzoic acids.8 Changes in photoelectron ionization potentials have been applied to geometrical studies of nitrobenzenes,90 phenols,9® anisóles,90 and disulfides. 26 In all cases the splitting between orbitals of appropriate symmetry is reduced when the geometry is perturbed from that which optimizes orbital overlap. Because the ionization potentials have been related to the cosine of the dimethylamino torsional angle,9a'b it is possible to use the chemical shifts to estimate these angles for other related compounds.…”