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Syntheses and Structure Determination of Trimethylsiloxy Functionalized Copper Chalcogenide Clusters
Author(s) -
Langer Robert,
Yu Wen,
Wünsche Linda,
Buth Gernot,
Fuhr Olaf,
Fenske Dieter
Publication year - 2011
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201100249
Subject(s) - selenide , chemistry , copper , chalcogenide , chalcogen , crystallography , cluster (spacecraft) , ligand (biochemistry) , crystal structure , selenium , organic chemistry , biochemistry , receptor , computer science , programming language
Four new copper chalcogenide clusters with trimethylsiloxy groups in the ligand shell have been synthesized and characterized by single‐crystal X‐ray diffraction. The compounds [Cu 22 Se 6 (S‐C 6 H 4 ‐OSiMe 3 ) 10 (PPh 3 ) 8 ] ( 1 ), [Cu 36 Se 8 (S‐C 6 H 4 ‐OSiMe 3 ) 20 (PPh 3 ) 8 ] ( 2 ) and [Cu 52 Se 20 (S‐C 6 H 4 ‐OSiMe 3 ) 12 (PPh 3 ) 11 ] ( 3 ) are core‐shell ‐cluster, in which the heavy atom frameworks are built up of a copper selenide core which is partly surrounded by a copper thiolate shell. They were synthesized by the reaction of CuOAc and PPh 3 with p ‐Me 3 SiS‐C 6 H 4 ‐OSiMe 3 and Se(SiMe 3 ) 2 in different ratios. The arrangements of the chalcogen atoms in 1 and 2 are similar to a close packing, while cluster 3 has a new unusual structural motif. In addition the analogous precursor p ‐Me 3 SiSe‐C 6 H 4 ‐OSiMe 3 was synthesized and investigated in the cluster synthesis. The reaction with CuOAc, PPh 3 and Se(SiMe 3 ) 2 leads to the formation of the functionalized copper selenide cluster [Cu 22 Se 6 (Se‐C 6 H 4 ‐OSiMe 3 ) 10 (PPh 3 ) 8 ] ( 4 ). This compound is similar to 1 and consists of a Cu 22 Se 16 core instead of a Cu 22 Se 6 S 10 core. The functionalization of the cluster compounds with trimethylsiloxy‐groups leads to a high solubility of these cluster.