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Issue 47, 2019
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Structural characterization and gas-phase studies of the [Ag10H8(L)6]2+ nanocluster dication

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Abstract

The reactions between silver salts and borohydrides produce a rich set of products that range from discrete mononuclear compounds through to silver nanoparticles and colloids. Previous studies using electrospray ionization mass spectrometry (ESI-MS) to track the cationic products in solutions containing sodium borohydride, silver(I) tetrafluoroborate and the bisphosphine ligands, L, bis(diphenylphosphino)methane (dppm) and bis(diphenylphosphino)amine (dppa) have identified the dications [Ag10H8(L)6]2+. Here we isolate and structurally characterize [Ag10H8(dppa)6](BF4)2, and [Ag10H8(dppa)6](NO3)2via X-ray crystallography. Both dications have nearly identical structural features consisting of a Ag10 scaffold with the atoms lying on vertices of a bicapped square antiprism. DFT calculations were carried out to suggest potential sites for the hydrides. Ion-mobility mass spectrometry experiments revealed that [Ag10H8(dppa)6]2+ and [Ag10H8(dppm)6]2+ have similar collision cross sections, while multistage mass spectrometry experiments were used to compare their unimolecular gas-phase chemistry. Although the same initial sequential ligand loss followed by cluster fission and H2 evolution is observed, the more acidic N–H of the dppa provides a more labile H for H2 loss and H/D scrambling processes as revealed by isotope labelled experiments.

Graphical abstract: Structural characterization and gas-phase studies of the [Ag10H8(L)6]2+ nanocluster dication

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Publication details

The article was received on 27 Sep 2019, accepted on 13 Nov 2019 and first published on 25 Nov 2019


Article type: Paper
DOI: 10.1039/C9NR08321A
Nanoscale, 2019,11, 22880-22889

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    Structural characterization and gas-phase studies of the [Ag10H8(L)6]2+ nanocluster dication

    H. Z. Ma, A. I. McKay, A. Mravak, M. S. Scholz, J. M. White, R. J. Mulder, E. J. Bieske, V. Bonačić-Koutecký and R. A. J. O'Hair, Nanoscale, 2019, 11, 22880
    DOI: 10.1039/C9NR08321A

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