Please use this identifier to cite or link to this item: https://apo.ansto.gov.au/dspace/handle/10238/7997
Title: Synthesis, Structural Characterization, and Gas-Phase Unimolecular Reactivity of the Silver Hydride Nanocluster [Ag3((PPh2)2CH2)3(μ3-H)](BF4)2.
Authors: Zavras, A
Khairallah, GN
Connell, TU
White, JM
Edwards, AJ
Mulder, RJ
O'Hair, RAJ
Donnelly, PS
Keywords: Mass spectroscopy
Neutron diffraction
Dissociation
Chemistry
Synthesis
Hydrides
Issue Date: 3-Jul-2014
Publisher: ACS Publications
Citation: Zavras, A., Khairallah, G. N., Connell, T. U., White, J. M., Edwards, A. J., Mulder, R. J., O’Hair, R. A. J. & Donnelly, P. S. (2014). Synthesis, structural characterization, and gas-phase unimolecular reactivity of the silver hydride nanocluster [Ag3((PPh2)2CH2)3(μ3-H)](BF4)2. Inorganic Chemistry, 53(14), 7429-7437. doi: 10.1021/ic5007499
Abstract: A 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–]. © 2014, American Chemical Society
Gov't Doc #: 7553
URI: http://doi: 10.1021/ic5007499
http://apo.ansto.gov.au/dspace/handle/10238/7997
ISSN: 0020-1669
Appears in Collections:Journal Articles

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