SCHEDULED MAINTENANCE
Structural characterization and gas-phase studies of the [Ag10H8(L)6]2+ nanocluster dication†
a
Antonija
Mravak,
b
Michael S.
Scholz,
a
Jonathan M.
White,
a
Roger J.
Mulder,
c
Evan J.
Bieske,
a
Richard A. J.
O'Hair
*a
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](/en/Image/Get?imageInfo.ImageType=GA&imageInfo.ImageIdentifier.ManuscriptID=C9NR08321A&imageInfo.ImageIdentifier.Year=2019)
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