English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Position-Space Bonding Indicators for Hexaborides of Alkali, Alkaline-Earth, and Rare-Earth Metals in Comparison to the Molecular Crystal K2[B6H6]

MPS-Authors
/persons/resource/persons126542

Börrnert,  C.
Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

/persons/resource/persons126626

Grin,  Y.
Juri Grin, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

/persons/resource/persons126896

Wagner,  F. R.
Frank Wagner, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

External Ressource
No external resources are shared
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available
Citation

Börrnert, C., Grin, Y., & Wagner, F. R. (2013). Position-Space Bonding Indicators for Hexaborides of Alkali, Alkaline-Earth, and Rare-Earth Metals in Comparison to the Molecular Crystal K2[B6H6]. Zeitschrift für Anorganische und Allgemeine Chemie, 639(11 Sp. Iss. SI), 2013-2024. doi:10.1002/zaac.201200514.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0015-1E56-D
Abstract
The crystal structure of the hexaborides MB6 of alkali, alkaline-earth, and rare-earth metals displays a network of interconnected B-6 octahedra, while isolated B6H6 units occur in the molecular crystal K-2[B6H6]. For the case of a total charge transfer of two electrons from the metal atoms, the B-6 units serve as classical examples of electron deficient clusters. QTAIM and ELI-D analyses of chemical bonding based on solid state DFT/APW+lo quantum chemical calculations were performed. Consistent with Wade's rules, a number of about seven endohedral bonds for the octahedral units is recovered from the delocalization index (DI). Detailed analyses of two- and three-center delocalization indices yield a clear two-center character of the exohedral B-B bonds and a mixed two- and three-center character of the endohedral B-B bonds. The picture obtained by topological analysis of ELI-D is in agreement with the DI results. With changing effective electron transfer from the metal atoms, electronic saturation of the intra-cluster bonding is found, which leads to the notion of generally two-valent rare-earth atoms in MB6 hexaborides.