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Functionalised Silver Chalcogenide Clusters
Author(s) -
Langer Robert,
Breitung Ben,
Wünsche Linda,
Fenske Dieter,
Fuhr Olaf
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.201100018
Subject(s) - chemistry , isostructural , trimethylsilyl , dimer , reactivity (psychology) , ligand (biochemistry) , chalcogenide , metal , crystallography , cluster (spacecraft) , crystal structure , medicinal chemistry , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology , computer science , programming language
Eight new silver chalcogenide clusters with different functional groups in the ligand shell were synthesised and characterised by single‐crystal X‐ray diffraction. The optical properties of the isostructural clusters [Ag 6 (S‐C 6 H 4 ‐CN) 6 (PPh 3 ) 6 ] ( 1 ) and [Ag 6 (S‐C 6 H 4 ‐NO 2 ) 6 (PPh 3 ) 6 ] ( 2 ) are described and compared. In addition, the reactivity of 1 towards metal salts and Lewis acids was investigated, which led to the compounds [Ag 6 (S‐C 6 H 4 ‐CN) 6 (PPh 3 ) 5 ] ( 3 ) and [Ag 14 S(S‐C 6 H 4 ‐CN) 12 (PPh 3 ) 8 ][FeCl 2 (thf) 4 ] 3 ( 4 ). The sulfur‐functionalised cluster [Ag 14 S(S‐C 6 H 4 ‐NCS) 12 (PPh 3 ) 8 ] ( 5 ) has prospects for further reactions and for the immobilisation on gold surfaces. The reactions of silver carboxylates with O,S‐bis(trimethylsilyl)‐4‐hydroxythiophenol and bis(trimethylsilyl) chalcogenides in the presence of tertiary phosphanes lead to the formation of the clusters [Ag 23 S 2 (S‐C 6 H 4 ‐OSiMe 3 ) 15 (S‐C 6 H 4 ‐OH) 3 (PPh 3 ) 8 ] ( 6 ) and [Ag 40 Se 4 (S‐C 6 H 4 ‐OSiMe 3 ) 32 (PPh 3 ) 8 ] ( 7 ). Compound 6 can be regarded as a dimer of the described Ag 14 ‐clusters in 4 and 5 , whereas the inorganic core of cluster 7 has an unusual curved structural motif. The reaction of AgOAc with 4‐hydroxothiophenol in the presence of triethylphosphane leads to the assembly of a three dimensional network of [Ag 8 (S‐C 6 H 4 ‐OH) 6 (PEt 3 ) 8 ](OAc) 2 ( 8 ) in the crystal structure. A solution of 8 was investigated by ESI mass spectrometry, which resulted in the detection of a series of polynuclear silver thiolates with the general composition [Ag n (S‐C 6 H 4 ‐OH) n –1 (PEt 3 ) 2 ] + .