Bond strengths in POCl3−, POCl2−, and PSCl2−

Abstract The bond strengths D (OCl 2 P − Cl) = 172 ± 7, D (OClP Cl − ) = 177 ± 8, and D (SClP Cl − ) = 186 ± 6 kJ mol −1 have been determined at 0 K by measuring thresholds for collision-induced dissociation in a flowing afterglow-tandem mass spectrometer. This thermochemistry is consistent with a close balance between dissociative and nondissociative electron capture for POCl 3 and PSCl 3 . B3LYP and G3 computational results give bond strengths lower by an average of about 20 kJ mol −1 .