Three bimetallic platinum/silver nanoclusters, PtAg 20 (dtp) 12 (1), Pt 2 Ag 33 (dtp) 17 (2), and Pt 3 Ag 44 (dtp) 22 (3) (dtp: dipropyl dithiophosphate), with cluster electron counts of 8, 16, and 22, respectively, were produced via a one-phase coreduction method. Singlecrystal X-ray structures reveal that their inner cores can be visualized as consisting of one, two, and three centered icosahedral Pt@Ag 12 units, respectively. In 2 and 3, these units are vertex-sharing and are assembled linearly. Intriguingly, the 22-electron alloy (3) is isolobal to the linear triiodide anion, I 3 − , and represents the first example of a cluster made of three superatoms whose bonding characteristics are similar to those of a triatomic molecular species.
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(O
n
Pr)2, 1;
dsep = Se2P(O
i
Pr)2, 2) describe a central platinum hydride (PtH) unit
encapsulated within a distorted Ag12 icosahedron, the resulting
(PtH)@Ag12 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, 1H and 195Pt 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@Ag12]5+ kernel can be viewed as a closed-shell superatomic core, the μ4-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 5dz
2(Pt) orbital.
Structurally precise palladium doped silver-nanoclusters [PdAg20] and [Pd6Ag14(S)] stabilized by twelve dithiophosphate ligands have been isolated. The latter is the first example where a hexa-palladium(0) core is embodied within a silver(i) cluster.
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