Abstract
The reactions of Pt+ and PtCl+ with Cl2, 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 Cl2 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 Cl2 are calculated using density functional theory.
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