Browsing by Author "White, JM"

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    Synthesis, structural characterization, and gas-phase unimolecular reactivity of the silver hydride nanocluster [Ag3((PPh2)2CH2)3(μ3-H)](BF4)2
    (ACS Publications, 2014-07-03) Zavras, A; Khairallah, GN; Connell, TU; White, JM; Edwards, AJ; Mulder, RJ; O'Hair, RAJ; Donnelly, PS
    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
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    Synthesis, structure and gas-phase reactivity of a silver hydride complex ag-3{(PPh2)(2)CH2}(3)(mu(3)-H)(mu(3)-Cl) BF4
    (John Wiley and Sons, 2013-08-05) Zavras, A; Khairallah, GN; Connell, TU; White, JM; Edwards, AJ; Donnelly, PS; O'Hair, RAJ
    Mass spectrometry shows the way! MS analysis of silver salts treated with sodium borohydride in the presence of a bis(phosphino) ligand revealed the formation of novel silver hydride nanocluster cations instead of all silver nanocluster cations. This serendipitous discovery prompted the condensed-phase synthesis, isolation, and characterization of [Ag3{(Ph2P)2CH2}3(μ3-H)(μ3-Cl)]BF4⋅0.5 CHCl3. © 2013, Wiley‐Vch Verlag.