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

Autori
Ma, Howard Z. ; McKay, Alasdair I. ; Mravak, Antonija ; Scholz, Michael S. ; White, Jonathan M. ; Mulder, Roger J. ; Bieske, Evan J. ; Bonačić-Koutecký, Vlasta ; O'Hair, Richard A. J.

Izvornik
Nanoscale (2040-3364) 11 (2019), 47; 22880-22889

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
XRD, DFT, isotopic labelling, ion mobility, gas phase fragmentation

Sažetak
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)2 via 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.

Izvorni jezik
Engleski

Znanstvena područja
Fizika, Kemija, Interdisciplinarne prirodne znanosti

POVEZANOST RADA