Scientists from CTI team of the Rennes Institute of Chemical Sciences (ISCR) and of the National Dong Hwa University (Taiwan) report in this work a hydride-doped eight-electron platinum/silver alloy nanocluster in which the hydride position is determined by neutron diffraction. The structures of [PtHAg19(dtp/desp)12] (dtp = S2P(OnPr)2; dsep = Se2P(OiPr)2) describe a central Pt-H unit encapsulated within a distorted Ag12 icosahedron, the resulting (PtH)@Ag12 core being stabilized by an outer sphere made up of 7 capping silver(I) atoms and 12 dichalcogenolates. DFT calculations indicate that the hydrogen electron participates to the superatom magic electron count of 8, but the 1s(H) AO does not contribute significantly to the construction of the four superatomic orbitals holding these electrons. Rather, it is involved in the building of a quite strong Pt-H sigma-bond. In other words, the main difference between the isoelectronic superatoms [PtHAg19(dtp)12] and [PtAg20(dtp)12]- is that an occupied non-bonding 5dz2(Pt) electron pair in the later is replaced by a Pt-H sigma bonding pair in the former.
Chiu, T.-H.; Liao, J.-H.; Gam, F.; Wu, Y.-Y.; Wang, X.; Kahlal, S.; Saillard, J.-Y.; Liu, C. W.
J. Am. Chem. Soc. 2022, doi.org/10.1021/jacs.2c03715
- Samia Kahlal, Univ Rennes, CNRS, ISCR-UMR 6226, F-35000 Rennes, France
samia [dot] kahlaluniv-rennes1 [dot] fr
- Jean-Yves Saillard, Univ Rennes, CNRS, ISCR-UMR 6226, F-35000 Rennes, France
jean-Yves [dot] saillarduniv-rennes1 [dot] fr
Published June 13, 2022