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Issue 10, 2019
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Solvent-free synthesis and reactivity of nickel(ii) borohydride and nickel(ii) hydride

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Transition metal-hydrides are highly useful in organic transformations of industrial importance yet synthesizing them or their precursor metal-borohydrides in high yield is cumbersome due to their high reactivity and sensitivity towards air and many common solvents. Reported is the development of a mechanochemical protocol for the solvent-free high-yield synthesis of nickel(II) borohydrides as precursors of nickel(II) hydrides. The Ni(II)-chelates (LHNi) were prepared by manually grinding Ni(II)-halides with a tetradentate macrocyclic N4 chelating ligand in the presence of air. The Ni(II)-chelates obtained were further ground with sodium borohydride to yield nickel(II)-borohydrides [LHNi(η2-BH4)]+, which in turn upon dissolution in solvents lost BH3 to yield homodinuclear nickel(II)-μ-hydrides [LHNi(μ-H)2NiL]2+. Representative reactions of the fully characterized nickel-hydride with alcohols, disulphides, benzyl bromide, trityl cation, air and SO2 yielding alkoxide, thiols, toluene, triphenylmethane, carbonate and sulfate, respectively, are presented. These results open a new avenue in handling sensitive borohydrides and provide a new route for high yield synthesis of hydrides and their precursors.

Graphical abstract: Solvent-free synthesis and reactivity of nickel(ii) borohydride and nickel(ii) hydride

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Supplementary files

Article information

28 Dec 2018
08 Apr 2019
First published
18 Apr 2019

Green Chem., 2019,21, 2752-2758
Article type

Solvent-free synthesis and reactivity of nickel(II) borohydride and nickel(II) hydride

S. Raje and R. Angamuthu, Green Chem., 2019, 21, 2752
DOI: 10.1039/C8GC04058C

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