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Issue 45, 2016
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Initial steps for the thermal decomposition of alkaline-earth metal amidoboranes: a cluster approximation

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Abstract

A DFT study of thermal decomposition mechanisms of [M(NH2BH3)2]4 clusters with M = Mg, Ca, and Sr is presented. Multi-step reaction pathways leading to elimination of the first H2 molecule are explored at the M06/TZVP level of theory. For all studied M, the clusters adopt similar structures and exhibit similar transformations along the reaction pathways. Their activation energies decrease in the order Mg < Ca ≤ Sr. Four metal atoms in the cluster form a rigid planar construction that is found to be nearly unchanged during all transformations. Cleavage of the B–H bond in the environment of alkaline-earth metal atoms leads to the “capture” of the released H atom by neighboring metal atoms with the formation of a M3H moiety. While the activation energies for the cleavage of Hδ can be as low as 14.3, 22.6 and 23.3 kcal mol−1 for M = Mg, Ca and Sr, respectively, barriers for the subsequent cleavage of Hδ+via destruction of the M3H moiety are about twice larger.

Graphical abstract: Initial steps for the thermal decomposition of alkaline-earth metal amidoboranes: a cluster approximation

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Publication details

The article was received on 23 Aug 2016, accepted on 19 Oct 2016 and first published on 20 Oct 2016


Article type: Paper
DOI: 10.1039/C6CP05835C
Phys. Chem. Chem. Phys., 2016,18, 31072-31077
  • Open access: Creative Commons BY license
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    Initial steps for the thermal decomposition of alkaline-earth metal amidoboranes: a cluster approximation

    A. V. Pomogaeva and A. Y. Timoshkin, Phys. Chem. Chem. Phys., 2016, 18, 31072
    DOI: 10.1039/C6CP05835C

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