Synthesis, Structural Characterization, and Gas-Phase Unimolecular Reactivity of the Silver Hydride Nanocluster [Ag3((PPh2)2CH2)3(μ3‑H)](BF4)2
dataset
posted on 2014-07-21, 00:00 authored by Athanasios Zavras, George N. Khairallah, Timothy U. Connell, Jonathan
M. White, Alison J. Edwards, Roger J. Mulder, Paul S. Donnelly, Richard A. J. O’HairA bis(diphenylphosphino)methane-ligated
trinuclear silver hydride
nanocluster, [Ag3((Ph2P)2CH2)3(μ3-H)](BF4)2, featuring three silver(I) ions coordinated to a μ3-hydride, and its deuteride analogue, [Ag3((Ph2P)2CH2)3(μ3-D)](BF4)2, have been isolated and structurally characterized
using electrospray ionization mass spectrometry (ESI-MS), X-ray crystallography,
NMR and IR spectroscopy. The position of the deuteride in [Ag3((Ph2P)2CH2)3(μ3-D)](BF4)2 was determined by neutron
diffraction. ESI-MS of [Ag3L3(μ3-H/D)](BF4)2 [L = ((Ph2P)2CH2)2] produces [Ag3L3(μ3-H/D)]2+ and [Ag3L3(μ3-H/D)(BF4)]+. A
rich gas-phase ion chemistry of [Ag3L3(μ3-H/D)]2+ is observed under conditions of collision-induced
dissociation (CID) and electron-capture dissociation (ECD). CID gives
rise to the following complementary ion pairs: [Ag3L2]+ and [L+(H/D)]+; [Ag2(H/D)L2]+ and [AgL]+; [Ag2(H/D)L]+ and [AgL2]+. ECD gives rise to a number
of dissociation channels including loss of the bis(phosphine) ligand,
fragmentation of a coordinated bis(phosphine) ligand via C–P
bond activation, and loss of a hydrogen (deuterium) atom with concomitant
formation of [Ag3L3]+. Under CID
conditions, [Ag3L3(μ3-H/D)(BF4)]+ fragments via ligand loss, the combined loss
of a ligand and [H,B,F4], and cluster fragmentation to
give [Ag2(BF4)L2]+ and
[Ag2(L-H)L]+ [where (L-H) = (Ph2P)2CH–].
