Ion–molecule reactions of W+ and WO+: new and improved values for IE(WO), D298(W+–O), D298(W–O) and ΔfH0298(WO)

The ICP/SIFT technique has been employed in bracketing measurements of the kinetics of selected electron-transfer reactions with WO+ and O-atom transfer reactions with W+. The measurements have provided more accurate values for IE(WO)=8.1 ± 0.3 eV (compared to the previously available value of 9.1 ± 1 eV) and D298(W+–O)=166 ± 10 kcal mol−1 (compared to the previously available value of 133 ± 35 kcal mol−1). These results lead to values for D298(W–O)=172 ± 17 kcal mol−1 and ΔfH0298(WO)=90 ± 17 kcal mol−1 which agree, within experimental uncertainty, with currently available values. The new experimental value for IE(WO)=8.1 ± 0.3 eV is in excellent agreement with the value of 8.05 ± 0.3 eV computed at the B3LYP/LanL2DZ/6-31+G* and at the B3LYP/sdd/6-31+G* levels of theory. A novel ring-opening reaction was observed between WO+ and pyrrole and the polysulfide cations WSn+1+ (n⩽5) and OWSn+1+ (n⩽4) were seen to be formed in sequential S-atom transfer reactions of OCS with W+ and WO+, respectively.