Structural characterization and gas-phase studies of the [Ag10H8(L)6]2+ nanocluster dication.
Howard Z MaAlasdair I McKayAntonija MravakMichael S ScholzJonathan M WhiteRoger J MulderEvan J BieskeVlasta Bonačić-KouteckýRichard A J O'HairPublished in: Nanoscale (2019)
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.
Keyphrases
- mass spectrometry
- quantum dots
- silver nanoparticles
- highly efficient
- liquid chromatography
- visible light
- ionic liquid
- high resolution
- gas chromatography
- ms ms
- multiple sclerosis
- gold nanoparticles
- density functional theory
- capillary electrophoresis
- high performance liquid chromatography
- magnetic resonance imaging
- single cell
- peripheral blood
- case control
- molecular dynamics
- magnetic resonance
- climate change
- molecular docking
- anaerobic digestion