Intemann J, Harder S, Sirsch P (2014)
Publication Status: Published
Publication Type: Journal article
Publication year: 2014
Publisher: Wiley-VCH Verlag
Book Volume: 20
Pages Range: 11204-11213
Journal Issue: 35
In analogy to the previously reported tetranuclear magnesium hydride cluster with a bridged dianionic bis-beta-diketiminate ligand, a related zinc hydride cluster has been prepared. The crystal structures of these magnesium and zinc hydride complexes are similar: the metal atoms are situated at the corners of a tetrahedron in which the vertices are bridged either by dianionic bis-b-diketiminate ligands or hydride ions. Both structures are retained in solution and show examples of H-center dot center dot center dot H- NMR coupling (Mg: 8.5 Hz; Zn: 16.0 Hz). The zinc hydride cluster [NN-(ZnH)(2)](2) thermally decomposes at 90 degrees C and releases 1.8 equivalents of H-2. In contrast to magnesium hydride clusters, there is no apparent relationship between cluster size and thermal decomposition temperature for the zinc hydrides. DFT calculations reproduced the structure of the zinc hydride cluster reasonably well and charge density analysis showed no bond paths between the hydride ions. This contrasts with calculations on the analogous magnesium hydride cluster in which a counter-intuitive H-center dot center dot center dot H- bond path was observed. Forcing a reduced H-center dot center dot center dot H- distance in the zinc hydride cluster, however, gave rise to a H-center dot center dot center dot H- bond path. Such weak interactions could play a role in H-2 desorption. The presumed molecular product after H-2 release, a Zn(I) cluster, could not be characterized experimentally but DFT calculations predicted a cluster with two localized Zn-Zn bonds.
APA:
Intemann, J., Harder, S., & Sirsch, P. (2014). Comparison of Hydrogen Elimination from Molecular Zinc and Magnesium Hydride Clusters. Chemistry - A European Journal, 20(35), 11204-11213. https://dx.doi.org/10.1002/chem.201402141
MLA:
Intemann, Julia, Sjoerd Harder, and Peter Sirsch. "Comparison of Hydrogen Elimination from Molecular Zinc and Magnesium Hydride Clusters." Chemistry - A European Journal 20.35 (2014): 11204-11213.
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