Journal of Physical Chemistry A, Vol.105, No.37, 8456-8464, 2001
Guided ion beam studies of the reactions of Fe+ and Co+ with CS2 and COS
The reactions of Fe+ and Co+ with CS2 and COS are studied using guided-ion beam mass spectrometry: Dominant products in all four systems are MS+ and MCX+ (X = S, O). Cross sections for forming FeCS+ and COCS+ in the CS2 systems exhibit two endothermic features, which are assigned to the formation of different structural isomers. From the thresholds associated with forming CoS+ and CoCS+, we determine Do(Co+-S) = 2.95 +/-0.09 eV and D-0(Co+-CS) = 2.68 +/- 0.34 eV. These values are compared with D-0(Fe+-S) = 3.08 +/- 0.04 eV and D-0(Fe+-CS) = 2.40 +/- 0.12 eV determined previously, and the differences are discussed in some detail. The results for both metal ions reacting with CXS (X = S, O) suggest that the initial step is predominantly insertion of the metal ion into the C-S bond, with activation of the stronger C-O bond being less likely. Comparison of the energy-dependent cross sections indicates that both the CS2 and COS systems show kinetic restrictions for Fe+, which do not occur with Co+. This difference can be attributed to changes of spin multiplicities in the various reactions, processes that are discussed in detail.