Synthesis, structure, and bonding of BaTl(3): an unusual competition between cluster and classical bonding in the thallium layers.
The new BaTl(3) compound has been synthesized and characterized by physical property measurements and electronic structure calculations. Its structure (Cmcm) is a new intermediate in the Ni(3)Sn family (P6(3)/mmc), and consists of thallium layers formed from two-center bond formation between the parallel chains of face-sharing octahedral clusters. The valence electron concentration (VEC) of the thallium layers is consistent with their two-dimensional nature, in comparison with those in other AX(3)-type compounds with one- or three-dimensional anionic networks with the same building blocks and different VECs. The unique geometric features of the anionic thallium layers bring on an unusual competition between inter- and intracluster bonds. Detailed studies of the energetics of BaTl(3) reveal for the first time the important role of cation-anion interactions in the bonding competition in such an anionic substructure.
Seo
Dong-Kyun
DK
Ames Laboratory-DOE and Department of Chemistry, Iowa State University, Ames, Iowa 50011, USA.
Corbett
John D
JD