Reactions of the gases SF6 and SF5Cl with the 1S ground state and 3D excited states of Cu+ were carried out in order to examine parameters influencing S-X (X=F,Cl) bond activation. Experiments were conducted using a selected ion drift cell apparatus. Both Cu+ states were prepared in a glow discharge utilizing Ne as the working gas. Ion mobility spectrometry (IMS) revealed state-specific product formation for both gases. Cu+(1S) reacts with both SF6 and SF5Cl to yield association products and is not observed to induce any bimolecular chemistry. Conversely, Cu+(3D) reacts with both compounds to yield SF3+, and with SF5Cl to form CuCl+. SF3+ does not appear to react further with either neutral reactant, whereas CuCl+ reacts in an efficient secondary process with SF5Cl to yield SF5+. Additional higher-order fragmentation products were observed to occur in trace amounts with both substrate molecules. Thermochemical requirements for fragmentation products in both reactions indicate that the neutral byproducts must involve some degree of bond formation to proceed exothermically. Candidates for possible product channels were evaluated on the basis of energetics and conservation of electron spin. State-specific kinetic measurements show that both Cu+ states are consumed efficiently by SF5Cl, whereas SF6 reacts with Cu+(1S,3D) slowly. This suggests that the rate-determining step in the SF5Cl reaction involves activation of the weaker S-Cl bond.

State-specific reactions of Cu+(1S,3D) with SF6 and SF5Cl: Thermochemical control over product formation

249th National Meeting (2015)

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