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Using electrospray ionization-tandem mass spectrometry to explore formation and gas-phase chemistry of silver nanoclusters generated from the reaction of silver salts with NaBH4 in the presence of bis(diphenylarsino)methane

Citation

Ma, HZ and McKay, AI and Canty, AJ and O'Hair, Richard AJ, Using electrospray ionization-tandem mass spectrometry to explore formation and gas-phase chemistry of silver nanoclusters generated from the reaction of silver salts with NaBH4 in the presence of bis(diphenylarsino)methane, Journal of Mass Spectrometry, 56, (4) Article e4590. ISSN 1076-5174 (2021) [Refereed Article]

Copyright Statement

Copyright 2020 John Wiley & Sons, Ltd.

DOI: doi:10.1002/jms.4590

Abstract

Electrospray ionization‐mass spectrometry (ESI‐MS) of mixtures of AgBF4 or AgNO3 with the capping ligand bis(diphenylarsino)methane ((Ph2As)2CH2 = dpam) in a solution of acetonitrile revealed the formation of the following cations: [Ag(CH3CN)(dpam)]+, [Ag(dpam)2]+, [Ag2(Cl)(dpam)2]+, and [Ag3(Cl)2(dpam)3]+. Addition of NaBH4 to these solutions results in the formation of the cluster cations [Ag2(BH4)(dpam)2]+, [Ag2(BH4)(dpam)3]+, [Ag3(H)(BH4)(dpam)3]+, [Ag3(BH4)2(dpam)3]+, [Ag3(H)(Cl)(dpam)3]+, and [Ag3(I)(BH4)(dpam)3]+, as established by ESI‐MS. Use of NaBD4 confirmed that borohydride is the source of the hydride in these clusters. An Orbitrap Fusion LUMOS mass spectrometer was used to explore the gas‐phase unimolecular chemistry of selected clusters via multistage mass spectrometry (MSn) experiments employing low‐energy collision‐induced dissociation (CID) and high‐energy collision‐induced dissociation (HCD) experiments. The borohydride containing clusters fragment via two competing pathways: (i) ligand loss and (ii) BH bond activation involving BH3 loss. Density functional theory (DFT) calculations were used to calculate the energetics of the optimized structures for all precursor ions, fragment ions, and neutrals and to estimate the reaction endothermicities. Generally, there is reasonable agreement between the most abundant product ion formed and the predicted endothermicity of the associated reaction channel. The DFT calculations predicted that the novel dimer [Ag2(BH4)(dpam)2]+ has a paddlewheel structure in which the dpam and BH4 ligands bridge both silver centers.

Item Details

Item Type:Refereed Article
Keywords:cluster, DFT, fragmentation, hydride, mass spectrometry, silver
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the physical sciences
UTAS Author:Canty, AJ (Professor Allan Canty)
ID Code:143456
Year Published:2021 (online first 2020)
Deposited By:Chemistry
Deposited On:2021-03-18
Last Modified:2021-04-14
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