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The Intermetalloid Cluster Cation (CuBi 8 ) 3+
Author(s) -
Knies Maximilian,
Kaiser Martin,
Isaeva Anna,
Müller Ulrike,
Doert Thomas,
Ruck Michael
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201703916
Subject(s) - bismuth , chemistry , monoclinic crystal system , crystallography , cluster (spacecraft) , copper , ionic liquid , intermetallic , ionic bonding , metal , inorganic chemistry , atom (system on chip) , ion , crystal structure , catalysis , organic chemistry , alloy , computer science , embedded system , programming language
The reaction of Bi, BiCl 3 , and CuCl in the ionic liquid [BMIm]Cl ⋅ 4 AlCl 3 (BMIm=1‐ n ‐butyl‐3‐methylimidazolium) at 180 °C yielded air‐sensitive shiny black crystals of (CuBi 8 )[AlCl 4 ] 2 [Al 2 Cl 7 ] and (CuBi 8 )[AlCl 4 ] 3 . For both compounds X‐ray diffraction on single crystals revealed monoclinic structures that contain the intermetalloid cluster (CuBi 8 ) 3+ . It is the first pure bismuth cluster with a 3d metal and the first with a metal that does not form binary intermetallics with bismuth under ambient pressure. The cluster can be interpreted either as a copper(I) cation, η 4 ‐coordinated by a square‐antiprismatic Bi 8 2+ polycation (Bi−Cu 267 pm), or as a nine‐atomic intermetalloid nido‐cluster with 22 skeletal electrons and the C 4 v symmetry. One of the chloride ions of a tetrahedral [AlCl 4 ] − group coordinates the copper atom (Cu−Cl 228 pm) and thereby completes its 18 electron count. DFT‐based calculations, followed by real‐space bonding analysis, revealed a multicenter bonding situation between copper and bismuth atoms with about seven shared electrons.