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[Ga 18 (Si t Bu 3 ) 8 ] and [Ga 22 (Si t Bu 3 ) 8 ]—Syntheses and Structural Characterization of Novel Gallium Cluster Compounds
Author(s) -
Donchev Alexander,
Schnepf Andreas,
Stößer Gregor,
Baum Elke,
Schnöckel Hansgeorg,
Blank Thomas,
Wiberg Nils
Publication year - 2001
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 - 10.1002/1521-3765(20010803)7:15<3348::aid-chem3348>3.0.co;2-8
Subject(s) - gallium , cluster (spacecraft) , metastability , metalloid , atom (system on chip) , crystallography , chemistry , bromide , cationic polymerization , stereochemistry , topology (electrical circuits) , inorganic chemistry , metal , organic chemistry , combinatorics , mathematics , computer science , embedded system , programming language
The novel neutral gallium cluster compounds [Ga 18 R* 8 ] ( 1 ) and [Ga 22 R* 8 ] ( 2 ) are obtained by warming up a metastable solution of gallium( I ) bromide in THF/C 6 H 5 CH 3 after addition of equimolar amounts of supersilyl sodium NaR* from −78 °C to room temperature (R*=Si t Bu 3 =supersilyl). From X‐ray structure analyses, the observed arrangements of the 18 and 22 Ga atoms in 1 and 2 , respectively, are comparable with an 18 atom section of the β ‐Ga modification, or show at least some kind of relationship to a 22 atom section of the Ga‐III modification. This allows a description of both the clusters as metalloid. The topology of the Ga atoms in 2 is also well explained by the Wade–Mingos rules as an eightfold capped closo ‐Ga 14 cluster, whereby the Ga atoms of Ga 14 occupy the center and the corners of a cuboctahedron with one Ga 3 face replaced by a Ga 4 face. Some concepts are presented about the formation mechanism, the cluster growth, and the metalloid character of the two Ga cluster compounds.