Issue 45, 2016

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

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

Supplementary files

Article information

Article type
Paper
Submitted
23 Aug 2016
Accepted
19 Oct 2016
First published
20 Oct 2016
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2016,18, 31072-31077

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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