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Synthesis, structure and gas-phase reactivity of the mixed silver hydride borohydride nanocluster [Ag33-H)(μ3-BH4)LPh3]BF4 (LPh = bis(diphenylphosphino)methane)


Zavras, A and Ariafard, A and Khairallah, GN and White, JM and Mulder, RJ and Canty, AJ and O'Hair, RAJ, Synthesis, structure and gas-phase reactivity of the mixed silver hydride borohydride nanocluster [Ag33-H)(μ3-BH4)LPh3]BF4 (LPh = bis(diphenylphosphino)methane), Nanoscale, 7, (43) pp. 18129-18137. ISSN 2040-3364 (2015) [Refereed Article]

Copyright Statement

Copyright 2015 The Royal Society of Chemistry

DOI: doi:10.1039/c5nr05690j


Borohydrides react with silver salts to give products that span multiple scales ranging from discrete mononuclear compounds through to silver nanoparticles and colloids. The cluster cations [Ag3(H)(BH4)L3]+ are observed upon electrospray ionization mass spectrometry of solutions containing sodium borohydride, silver(I) tetrafluoroborate and bis(dimethylphosphino)methane (LMe) or bis(diphenylphosphino)methane (LPh). By adding NaBH4 to an acetonitrile solution of AgBF4 and LPh, cooled to ca. −10 C, we have been able to isolate the first mixed silver hydride borohydride nanocluster, [Ag33-H)(μ3-BH4)LPh3]BF4, and structurally characterise it via X-ray crystallography. Combined gas-phase experiments (LMe and LPh) and DFT calculations (LMe) reveal how loss of a ligand from the cationic complexes [Ag3(H)(BH4)L3]+ provides a change in geometry that facilitates subsequent loss of BH3 to produce the dihydride clusters, [Ag3(H)2Ln]+ (n = 1 and 2). Together with the results of previous studies (Girod et al., Chem. Eur. J., 2014, 20, 16626), this provides a direct link between mixed silver hydride/borohydride nanoclusters, silver hydride nanoclusters, and silver nanoclusters.

Item Details

Item Type:Refereed Article
Keywords:nanoscale, polynuclear, silver aggregates, computational chemistry, mass spectrometry, borohydride, hydride complexes
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
UTAS Author:Canty, AJ (Professor Allan Canty)
ID Code:104953
Year Published:2015
Web of Science® Times Cited:24
Deposited By:Chemistry
Deposited On:2015-11-30
Last Modified:2018-03-14

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