High- and Low-Temperature Modifications of Sc3RuC4 and Sc3OsC4—Relativistic Effects, Structure, and Chemical Bonding
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- 作者：Christian Vogt ; Rolf-Dieter Hoffmann ; Ute Ch. Rodewald ; Georg Eickerling ; Manuel Presnitz ; Volker Eyert ; Wolfgang Scherer ; Rainer Pttgen
- 刊名：Inorganic Chemistry
- 出版年：2009
- 出版时间：July 20, 2009
- 年：2009
- 卷：48
- 期：14
- 页码：6436-6451
- 全文大小：1434K
- 年卷期：v.48,no.14(July 20, 2009)
- ISSN：1520-510X
文摘
Sc3RuC4 and Sc3OsC4 were synthesized by arc-melting and subsequent annealing. At room temperature, they crystallize with the Sc3CoC4 structure, space group Immm. At 223 and 255 K, Sc3RuC4 and Sc3OsC4, respectively, show a monoclinic distortion caused by a pair-wise displacement of the one-dimensional [Ru(C2)2]δ− and [Os(C2)2]δ− polyanions, which are embedded in a scandium matrix. Superstructure formation leads to shorter Ru−Ru and Os−Os distances of 316 pm between adjacent [Ru(C2)2]δ− and [Os(C2)2]δ− polyanions. Each ruthenium (osmium) atom is covalently bonded to four C2 pairs with Ru−C (Os−C) distances of 220−222 pm. A comparison of the C−C bond distances at room temperature in Sc3TC4 with T representing a group 8 transition metal (Fe, Ru, Os) reveals a minimum in the case of the 4d metal Ru: 144.98(11) pm (Fe), 142.8(7) pm (Ru), and 144.6(4) pm (Os). Analysis of the local electronic structure of the [T(C2)2] moieties hints at a complex interplay between chemical bonding and relativistic effects, which is responsible for the V-shaped pattern of the C−C bond distances (long, short, and long for T = Fe, Ru, and Os, respectively). Relativistic effects lead to a strengthening of covalent T−C bonding. This is shown on the basis of periodic DFT calculations by a significant increase of the charge density at the T−C bond critical points (0.55 < 0.57 < 0.64 eÅ−3) down the row of group 8 elements. These structural characteristics and topological features do not change in the corresponding low-temperature phases of Sc3RuC4 and Sc3OsC4. However, topological analyses of theoretical charge density distributions reveal distinct changes of the valence shell charge concentrations at the transition metal centers due to the monoclinic distortions. Presumably, the local electronic situation at the transition metals reflects the origin and extent of these monoclinic distortions.