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Issue 4, 2017
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Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H2S)n+ clusters in the gas phase

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Abstract

A two-center three-electron 2c–3e bond (hemi-bond) is a non-classical chemical bond, and its existence has been supposed in radical cation clusters with lone pairs. Though the nature of the hemi-bond and its role in the reactivity of radical cations have attracted great interest, spectroscopic observations of hemi-bonded structures have been very scarce. In the present study, the presence of a stable hemi-bonded core (H2S∴SH2)+ in (H2S)n+ (n = 3–6) in the gas phase is demonstrated by infrared spectroscopy combined with quantum chemical calculations. The spectral features of the free SH stretch of the ion core show that the hemi-bond motif of the ion core is maintained up to the completion of the first H-bonded solvation shell. All of the observed spectra are well reproduced by the minimum energy hemi-bonded isomers, and no sign of the proton-transferred ion core type H3S+–SH, which is estimated to have a much higher energy, is found. Spin density calculations show that the excess charge is almost equally delocalized over the two H2S molecules in the cluster for n = 3 to 6. This also indicates the hemi-bond nature of the (H2S∴SH2)+ ion core and the small impact of the formation of a solvation shell on the ion core.

Graphical abstract: Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H2S)n+ clusters in the gas phase

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Publication details

The article was received on 07 Dec 2016, accepted on 09 Jan 2017, published on 11 Jan 2017 and first published online on 11 Jan 2017


Article type: Edge Article
DOI: 10.1039/C6SC05361K
Citation: Chem. Sci., 2017,8, 2667-2670
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    Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H2S)n+ clusters in the gas phase

    D. Wang and A. Fujii, Chem. Sci., 2017, 8, 2667
    DOI: 10.1039/C6SC05361K

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