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Issue 8, 2005
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Monitoring reagent modification of charged SnxOy nanoclusters using Fourier transform ion cyclotron mass spectrometry

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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:PA (Sn2O3) > PA (SnO2) ≫ PA (Sn3O4) > PA (Sn5O6) ≈ PA (Sn6O7) ≈ PA (CH3O) = 381 ± 2 kcal mol−1 > PA (Sn) = 352 ± 10 kcal mol−1Ion–molecule reaction results for the hypermetallic cations x = 2–5 with CH3OH are suggestive of gas-phase coordination chemistry, with each cluster undergoing one slow association reaction. A recurrent theme of the chemistry of ionic SnxOy is the initial activation or generation of OySnx−/+–OH bonds by a radical mechanism involving hydrogen or hydroxyl abstraction from the reagent. The resulting cluster-hydroxyl bonds are relatively labile with respect to conversion to alkoxy ligands.

Graphical abstract: Monitoring reagent modification of charged SnO nanoclusters using Fourier transform ion cyclotron mass spectrometry

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Publication details

The article was received on 07 Dec 2004, accepted on 01 Mar 2005 and first published on 16 Mar 2005


Article type: Paper
DOI: 10.1039/B418340A
Citation: Phys. Chem. Chem. Phys., 2005,7, 1687-1693
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    Monitoring reagent modification of charged SnxOy nanoclusters using Fourier transform ion cyclotron mass spectrometry

    P. Jackson, K. J. Fisher and G. D. Willett, Phys. Chem. Chem. Phys., 2005, 7, 1687
    DOI: 10.1039/B418340A

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