Monitoring reagent modification of charged SnxOy nanoclusters using Fourier transform ion cyclotron mass spectrometry
Abstract
The ion–molecule reactions of laser-generated radical clusters SnxOx+1−
(x
= 1–6), SnxOx−1+
(x
= 1–6) and SnxOx+
(x
= 2, 3) with the reagents H2S and CH3OH have been investigated using FTICR-MS. For the hypermetallic cations SnxOx−1+, the rates of the sulfur-for-oxygen substitution reactions with H2S appear to be sensitive to LDA/DFT-predicted oxygen binding modes, with μ3-O modes relatively inert with respect to μ-O conformations. The reactions of the hypometallic anions SnxOx+1− with H2S were dominated by proton transfer, although S-for-O substitution was observed to be kinetically competitive. The rates of the proton transfer were found to vary with both the reagent and cluster anion, and an analysis of the reaction kinetics for SnxOx+1− afforded the relative cluster proton affinities: