Synthesis, structure and gas-phase reactivity of the mixed silver hydride borohydride nanocluster [Ag3(μ3-H)(μ3-BH4)LPh3]BF4 (LPh = bis(diphenylphosphino)methane)

Athanasios Zavras; Alireza Ariafard; George N. Khairallah; Jonathan M. White; Roger J. Mulder; Allan J. Canty; Richard A. J. O'Hair

doi:10.1039/C5NR05690J

Synthesis, structure and gas-phase reactivity of the mixed silver hydride borohydride nanocluster [Ag₃(μ₃-H)(μ₃-BH₄)L^Ph₃]BF₄ (L^Ph = bis(diphenylphosphino)methane)†

Athanasios Zavras,^a Alireza Ariafard,^abc George N. Khairallah,^a Jonathan M. White,^a Roger J. Mulder,^d Allan J. Canty^b and Richard A. J. O'Hair*^a

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* Corresponding authors

^a School of Chemistry and Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Melbourne, Victoria 3010, Australia
E-mail: rohair@unimelb.edu.au

^b The School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia

^c Department of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University, Shahrak Gharb, Tehran, Iran

^d CSIRO Manufacturing, Bayview Avenue, Clayton, VIC 3168, Australia

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^Ph₃]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)₂L_n]⁺ (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.

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DOI: https://doi.org/10.1039/C5NR05690J
Article type: Paper
Submitted: 21 Aug 2015
Accepted: 05 Oct 2015
First published: 16 Oct 2015
This article is Open Access

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Nanoscale, 2015,7, 18129-18137

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Synthesis, structure and gas-phase reactivity of the mixed silver hydride borohydride nanocluster [Ag₃(μ₃-H)(μ₃-BH₄)L^Ph₃]BF₄ (L^Ph = bis(diphenylphosphino)methane)

A. Zavras, A. Ariafard, G. N. Khairallah, J. M. White, R. J. Mulder, A. J. Canty and R. A. J. O'Hair, Nanoscale, 2015, 7, 18129 DOI: 10.1039/C5NR05690J

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