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Ti2Rh6B – a new boride with a double perovskite-like structure containing octahedral Rh6 clusters

✍ Scribed by Fokwa, Boniface P. T.; Eck, Bernhard; Dronskowski, Richard

Book ID: 120650194
Publisher: Oldenbourg Wissenschaftsverlag
Year: 2006
Tongue: English
Weight: 223 KB
Volume: 221
Category: Article
ISSN: 2194-4946
DOI: 10.1524/zkri.2006.221.5-7.445

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✦ Synopsis

Abstract

Single crystals of Ti~2~Rh~6~B were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. The new silver-like compound with metallic luster crystallizes in space group Fm-3__m__ (no. 225) with a = 7.8191(5) Å, V = 478.05(5) Å^3^, and Z = 4. The refinement converged to R
~1~ = 0.0169 and wR
~2~ = 0.0486 for all 96 unique reflections and 7 parameters. The structure can be described as a defect double perovskite, A~2~BB'O~6~, where the A site is occupied by titanium, the B site by boron, the O site by rhodium but the B' site is vacant leading to the formation of perfectly octahedral Rh~6~ clusters and BRh~6~ units. Rh—B, Rh—Ti, and Rh—Rh interactions are observed. According to density-functional (LMTO) electronic structure calculations, the strongest bonding occurs for the Rh—B contacts, and the Rh—Rh bonding within the clusters is more than two times stronger than in the BRh~6~ units.

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