화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.126, No.43, 14123-14128, 2004
Covalently bonded (1)(infinity)[Pt](-) chains in BaPt: Extension of the Zintl-Klemm concept to anionic transition metals?
BaPt has been synthesized by reaction of a 1:1 mixture of Ba and Pt at 1223 K in argon and characterized by single-crystal X-ray structure determination and electrical resistivity and magnetic susceptibility measurements. The compound crystallizes in the NiAs structure type with an extremely low value for the c/a ratio (hexagonal space group P6(3)/mmc with a = 5.057(2) Angstrom, c = 5.420(3) Angstrom, c/a = 1.072, R1 = 0.0297, N-hkl = 93). This c/a ratio reflects structural features that are unusual for the NiAs type: Pt is coordinated linearly by two other Pt atoms at a distance as short as 2.71 Angstrom, thus forming a chain along [001] of homonuclearly bonded platinum. Band structure calculations and electron localization function analyses reveal a covalent character of Pt-Pt interactions along the c axis and two-dimensional metallic conductivity parallel to the ab plane. In terms of the Zintl-Klemm concept, in its most general sense, BaPt can be formulated as (Ba2+)((1)(infinity)[Pt](-))(.)e(-), and it can be considered a new example of platinide anions in the solid state.