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

The bond strengths D(OCl2P−Cl) = 172 ± 7, D(OClPCl−) = 177 ± 8, and D(SClPCl−) = 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 POCl3 and PSCl3. B3LYP and G3 computational results give bond strengths lower by an average of about 20 kJ mol−1.