Guided ion beam and ab initio studies of platinum chloride cations

The reactions of Pt+ and PtCl+ with Cl-2, ligand exchange reactions of PtCl+ and PtCl2+ with CO, and collision-induced dissociation (CID) of PtCl+, PtCl2+, and PtClCO+ are studied in a guided ion beam tandem mass spectrometer. The reactions with Cl-2 are exothermic and efficient at thermal energies, producing PtCl+ and PtCl2+, respectively. The ligand exchange reactions of PtCl+ yield PtCO+ and of PtCl2+ produce PtClCO+ and PtCO+, all in endothermic processes. In addition, PtCl2+ reacts with CO to form C-Cl bonds yielding both Cl2CO and ClCO. The kinetic energy dependence of these reactions and of the CID processes are analyzed to yield bond dissociation energies (BDEs) at 0 K for Pt+-Cl and ClPt+-Cl, 2.55 +/- 0.15 and 2.67 +/- 0.19 eV, respectively, along with BDEs for Cl-CO of 0.74 +/- 0.20 eV and for Cl-COCl of 2.82 +/- 0.20 eV. The structures and energetics of the PtCl+ and PtCl2+ molecules and the potential energy surface for the reaction of Pt+ with Cl-2 are calculated using density functional theory.