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Article Dans Une Revue Journal of the American Chemical Society Année : 2022

Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies

Résumé

Recent reports on hydride-doped noble metal nanoclusters strongly suggest that the encapsulated hydride is a part of the superatom core, but no accurate location of the hydride could be experimentally proved, so far. We report herein a hydride-doped eight-electron platinum/silver alloy nanocluster in which the position of four-coordinated hydride was determined by neutron diffraction for the first time. X-ray structures of [PtHAg19(dtp/desp)(12)] (dtp = S2P((OPr)-Pr-n)(2), 1; dsep = Se2P((OPr)-Pr-i)(2), 2) describe a central platinum hydride (PtH) unit encapsulated within a distorted Ag-12 icosahedron, the resulting (PtH)@Ag-12 core being stabilized by an outer sphere made up of 7 capping silver atoms and 12 dichalcogenolates. Solid-state structures of 1 and 2 differ somewhat in the spatial configuration of their outer spheres, resulting in overall different symmetries, C-1 and C-3, respectively. Whereas the multi-NMR spectra of 2 in solution at 173 K reveal that the structure of C-3 symmetry is the predominant one, H-1 and Pt-195 NMR spectra of 1 at the same temperature disclose the presence of isomers of both C-1 and C-3 symmetry. DFT calculations found both isomers to be very close in energy, supporting the fact that they co-exist in solution. They also show that the [PtH@Ag-12](5+) kernel can be viewed as a closed-shell superatomic core, the mu(4)-hydride electron contributing to its eight-electron count. On the other hand, the 1s(H) orbital contributes only moderately to the superatomic orbitals, being mainly involved in the building of a Pt-H bonding electron pair with the 5d(z)(2)(Pt) orbital.
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Dates et versions

hal-03715367 , version 1 (11-05-2023)

Identifiants

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Tzu-Hao Chiu, Jian-Hong Liao, Franck Gam, Ying-Yann Wu, Xiaoping Wang, et al.. Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies. Journal of the American Chemical Society, 2022, 144 (23), pp.10599-10607. ⟨10.1021/jacs.2c03715⟩. ⟨hal-03715367⟩
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