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Updated: Jun 26, 2026

Supercritical Nitrogen Processing for the Purification of Reactive Porous Materials
Published on: May 15, 2015
Structures and aggregation of the methylamine-borane molecules, Me(n)H(3-n)N.BH(3) (n = 1-3), studied by X-ray
Simon Aldridge1, Anthony J Downs, Christina Y Tang
1Inorganic Chemistry Laboratory, University of Oxford, UK.
Abstract:
The structures of the molecules methylamine-borane, MeH(2)N.BH(3), and dimethylamine-borane, Me(2)HN.BH(3), have been investigated by gas-phase electron diffraction (GED) and quantum chemical calculations. The crystal structures have also been determined for methylamine-, dimethylamine-, and trimethylamine-borane, Me(n)H(3-n)N.BH(3) (n = 1-3); these are noteworthy for what they reveal about the intermolecular interactions and, particularly, the N-H...H-B dihydrogen bonding in the cases where n = 1 or 2. Hence, structures are now known for all the members of the ammonia- and amine-borane series Me(n)H(3-n)N.BH(3) (n = 0-3) in both the gas and solid phases. The structural variations and energetics of formation of the gaseous adducts are discussed in relation to the basicity of the Me(n)H(3-n)N fragment. The relative importance of secondary interactions in the solid adducts with n = 0-3 has been assessed by the semi-classical density sums (SCDS-PIXEL) approach.
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Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.