Hydride-Containing Eight-Electron Pt/Ag Superatoms

November 22, 2022
(Left) Neutron structure of the μ4-hydride enclosed in the Ag12 icosahedral skeleton of [PtHAg19(dtp)12], where dtp = S2P(OnPropyl)2. (Right) The four-coordinated hydride.

Scientific Achievement

The study established the existence and solved the structure of a four-coordinated (m4) hydride doped eight-electron platinum/silver superatom nanocluster in the material PtHAg19(dtp)12.

Significance and Impact

Hydride-bearing superatoms offer stable and unique catalytic behavior that have attracted great research interest. Determination of hydride position in the superatom’s structure provides the key to predicting its behavior and designing useful reactions.

Research Details

  • X-ray and neutron diffraction determined the crystal structure and position of the four-coordinated hydride in the superatom nanocluster.
  • Nuclear magnetic resonance (NMR) spectroscopy confirmed the hydride’s presence and further identified how it fits into the cavity of the outer structure.
  • Density functional theory (DFT) calculation shows that the [PtH@Ag12]5+ kernel can be viewed as a closed-shell superatomic core, the μ4-hydride electron contributing to its eight-electron count.

"Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies"
Tzu-Hao Chiu, Jian-Hong Liao, Franck Gam, Ying-Yann Wu, Xiaoping Wang, Samia Kahlal, Jean-Yves Saillard and C. W. Liu,
Journal of the American Chemical Society, 144, 10599-10607 (2022). DOI: https://doi.org/10.1021/jacs.2c03715