Bond dissociation energies of the diatomic late transition metal sulfides: RuS, OsS, CoS, RhS, IrS, and PtS.

Abstract

The spectra of RuS, OsS, CoS, RhS, IrS, and PtS have been recorded near their respective bond dissociation energies using resonant two-photon ionization spectroscopy. The spectra display an abrupt drop to baseline when the bond dissociation energy (BDE) is exceeded. It is argued that spin-orbit and nonadiabatic interactions among the myriad of states that result from the ground and low-lying separated atom limits cause the molecules to predissociate rapidly as soon as the ground separated atom limit is exceeded in energy. Thus, the observed sharp predissociation thresholds are assigned as the 0 K BDEs of the molecules. With this assumption, the BDEs are assigned as follows: 4.071(8) eV (RuS), 4.277(3) eV (OsS), 3.467(5) eV (CoS), 3.611(3) eV (RhS), 4.110(3) eV (IrS), and 4.144(8) eV (PtS). Using thermochemical cycles, the gas-phase enthalpies of formation at 0 K, ΔfH0 K°, were calculated to be 531.8(4.3) kJ mol-1 (RuS), 651.2(6.3) kJ mol-1 (OsS), 365.3(2.2) kJ mol-1 (CoS), 481.5(2.1) kJ mol-1 (RhS), 546.7(6.3) kJ mol-1 (IrS), and 438.9(1.5) kJ mol-1 (PtS). The ionization energies of RuS, CoS, and RhS were also calculated using data on the BDEs of the associated cations and were found to be 8.39(10) eV (RuS), 8.40(9) eV (CoS), and 8.46(12) eV (RhS). Combining these data with predissociation measurements of other transition metal sulfide BDEs, the periodic trends in the transition metal sulfide BDEs are discussed and the BDEs of the transition metal sulfides are compared to those of the corresponding selenides. The BDEs of the sulfides are found to be 15.4% greater than those of the corresponding sulfides.