Abstract
Thermal reactions of Fe(CS2)n+ (n = 1, 2) with a series of ligand molecules, L, have been studied by using a selected ion flow tube. Primary reactions observed include ligand association, ligand switching, and charge transfer. Fe(CS2)+ favors association while Fe(CS2)2+ undergoes mainly switching reactions. The bond dissociation energy D°(Fe+−CS2) = 39.6 ± 2.5 kcal/mol was determined by the measurement of forward and backward ligand switching rate constants. This value was verified by the observation of the onset of switching for a series of reactions Fe(CS2)+ + L → FeL+ + CS2 as a function of D°(Fe+−L). Consecutive reactions in the flow tube tend to produce end products having a maximum coordination number of four, e.g., Fe(CS2)L3+ and Fe(L)4+, where L is a monodentate ligand such as NH3 or Fe(L)2+ with polydentate ligands such as C6H6. The interactions of Fe(CS2)+ and Fe(CS2)2+ with Xe were studied using a guided ion beam apparatus. Collision-induced dissociation (CID) thresholds gave bond dissociation ...
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