Issue 4, 2016

s-Block amidoboranes: syntheses, structures, reactivity and applications


Metal amidoborane compounds of the alkali- and alkaline earth metals have in recent years found applications in diverse disciplines, notably as hydrogen storage materials, as reagents for the reduction of organic functional groups and as catalysts and intermediates in dehydrocoupling reactions. These functions are connected by the organometallic chemistry of the MNR2BH3 group. This review focusses on central aspects of the s-block amidoborane compounds – their syntheses, structures and reactivity. Well-defined amidoborane complexes of group 2 metals are now available by a variety of solution-phase routes, which has allowed a more detailed analysis of this functional group, which was previously largely confined to solid-state materials chemistry. Structures obtained from X-ray crystallography have begun to provide increased understanding of the fundamental steps of key processes, including amine–borane dehydrocoupling and hydrogen release from primary and secondary amidoboranes. We review structural parameters and reactivity to rationalise the effects of the metal, nitrogen substituents and supporting ligands on catalytic performance and dehydrogenative decomposition routes. Mechanistic features of key processes involving amidoborane compounds as starting materials or intermediates are discussed, alongside emerging applications such as the use of group 1 metal amidoboranes in synthesis. Finally, the future prospects of this vibrant branch of main group chemistry are evaluated.

Graphical abstract: s-Block amidoboranes: syntheses, structures, reactivity and applications

Article information

Article type
Review Article
10 Jul 2015
First published
30 Nov 2015
This article is Open Access
Creative Commons BY license

Chem. Soc. Rev., 2016,45, 1112-1128

Author version available

s-Block amidoboranes: syntheses, structures, reactivity and applications

T. E. Stennett and S. Harder, Chem. Soc. Rev., 2016, 45, 1112 DOI: 10.1039/C5CS00544B

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