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Journal of Alloys and Compounds, Volume 618, 2015, Pages 299–304.
Frank Tambornino, Constantin Hoch.
Department Chemie und Pharmazie, Ludwig-Maximilians-Universität München, Butenandtstraße 5-13 (D), D-81377 München, Germany.
Abstract
The new mercury-rich amalgam KHg6 crystallises with the BaHg6 structure type (orthorhombic, space group Pnma (No. 62), a = 13.394(9) Å, b = 5.270(3) Å, c = 10.463 Å). It was prepared by electrolysis of a solution of KI in N,N′-Dimethylformamide at 343 K at a reactive Hg cathode. The structure of KHg6 shows motifs of ionic packing, covalent Hg cluster formation and metallic properties. KHg6 decomposes peritectically at 443 K. The combination of alkali metals with a noble metal with moderate electron affinity results in the formation of polar metal–metal bonding with considerable but incomplete electron transfer from the electropositive to the electronegative sublattice, resulting in typical “bad metal behaviour”, illustrated by resistance and susceptibility measurements and quantum theoretical calculations.
