title: Synthesis, structure and gas-phase reactivity of the mixed silver hydride borohydride nanocluster [Ag3(μ3-H)(μ3-BH4)L(Ph)3]BF4 (L(Ph) = bis(diphenylphosphino)methane).
abstract: 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 (L(Me)) or bis(diphenylphosphino)methane (L(Ph)). By adding NaBH4 to an acetonitrile solution of AgBF4 and L(Ph), cooled to ca. -10 °C, we have been able to isolate the first mixed silver hydride borohydride nanocluster, [Ag3(μ3-H)(μ3-BH4)L(Ph)3]BF4, and structurally characterise it via X-ray crystallography. Combined gas-phase experiments (L(Me) and L(Ph)) and DFT calculations (L(Me)) 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.
authors.affiliation: School of Chemistry and Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Melbourne, Victoria 3010, Australia. rohair@unimelb.edu.au.
authors.forename: Athanasios
authors.initials: A
authors.lastname: Zavras
authors.affiliation: School of Chemistry and Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Melbourne, Victoria 3010, Australia. rohair@unimelb.edu.au and The School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia.
authors.forename: Alireza
authors.initials: A
authors.lastname: Ariafard
authors.affiliation: School of Chemistry and Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Melbourne, Victoria 3010, Australia. rohair@unimelb.edu.au.
authors.forename: George N
authors.initials: GN
authors.lastname: Khairallah
authors.affiliation: School of Chemistry and Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Melbourne, Victoria 3010, Australia. rohair@unimelb.edu.au.
authors.forename: Jonathan M
authors.initials: JM
authors.lastname: White
authors.affiliation: CSIRO Manufacturing, Bayview Avenue, Clayton, VIC 3168, Australia.
authors.forename: Roger J
authors.initials: RJ
authors.lastname: Mulder
authors.affiliation: The School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia.
authors.forename: Allan J
authors.initials: AJ
authors.lastname: Canty
authors.affiliation: School of Chemistry and Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Melbourne, Victoria 3010, Australia. rohair@unimelb.edu.au.
authors.forename: Richard A J
authors.initials: RA
authors.lastname: O'Hair