Potential Energy Surface of SCl₃^-

Abstract

Sulfur trichloride anion is stable in the gas phase. Computational results at the G2 level indicate that SCl 3lies 99.0 kJ/mol below the dissociation products, dichlorosulfide and chloride anion, on a single-well potential energy surface. The anion has a T shape, with axial S-Cl bond lengths of 2.383 Å and an equatorial S-Cl bond length of 2.068 Å. Collision-induced dissociation results obtained using a flowing afterglow-tandem mass spectrometer give a D O (SCl 2 -Cl -) bond energy of 85 ( 8 kJ/mol.

The thermochemistry of group 15 tetrachloride anions

“…Ϫ are 101 Ϯ 8 [23], 90 Ϯ 7, 85 Ϯ 8 [45], and 99 Ϯ 5 kJ/mol [11], respectively. All of these values are equal within their combined uncertainties.…”

5 Gas-phase stabilities of small anions

“…The reaction profiles for hetero-atom substitution can be strongly at variance with those of S N 2 reactions. Gailbreath et al 90 have investigated the Cl 2 + SCl 2 ? SCl 2 + Cl 2 reaction in a flowing afterglow mass spectrometer as well as by accompanying calculations.…”

The Importance of Hydration Thermodynamics in Fragment‐to‐Lead Optimization

“…Previous studies20, 22, 23 of nucleophilic substitution at sulfur have indicated that the B3LYP method properly describes well depths and barrier heights. All structures (without the presence of FAD) were completely optimized at the B3LYP/6‐31+G* level of theory and the energies were estimated by using single points at B3LYP/6‐31++G** level of theory.…”

“…The addition reaction is not energetically demanding and yields a stable intermediate. A good example of this is the addition of Cl − to SCl 2 to form the highly stable SCl 3 − intermediate, which occurs without an energy barrier 23. Herein, we use the reaction of cyclo‐ L ‐cystine with thiolate to study the mechanism with and without the presence of FAD to investigate whether the barrier of the elimination step is reduced by the presence of the cofactor.…”