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Heteropolynuclear Complexes with the Ligand Ph 2 PCH 2 SPh: Theoretical Evidence for Metallophilic Au−M Attractions
Author(s) -
Fernández Eduardo J.,
LópezdeLuzuriaga José M.,
Monge Miguel,
Rodríguez Miguel A.,
Crespo Olga,
Gimeno M. Concepción,
Laguna Antonio,
Jones Peter G.
Publication year - 2000
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/(sici)1521-3765(20000218)6:4<636::aid-chem636>3.0.co;2-a
Subject(s) - tetrahydrothiophene , chemistry , phosphine , molar ratio , ligand (biochemistry) , crystallography , metal , stereochemistry , medicinal chemistry , catalysis , organic chemistry , biochemistry , receptor
Addition of two equivalents of diphenylthiomethylphosphine (PPh 2 CH 2 SPh) to the starting materials [Au(tht) 2 ]A (tht=tetrahydrothiophene), AgCF 3 SO 3 , or [Cu(CH 3 CN) 4 ]CF 3 SO 3 produces the mononuclear derivatives [M(PPh 2 CH 2 SPh) 2 ]A (M=Au, A=CF 3 SO 3 ( 1 a ); M=Au, A=ClO 4 ( 1 b ); M=Ag, A=CF 3 SO 3 ( 4 ); M=Cu, A=CF 3 SO 3 ( 5 )) which are able to form the heterodinuclear complexes [AuM′(PPh 2 CH 2 SPh) 2 ](CF 3 SO 3 ) 2 (M′=Ag ( 2 ), Cu ( 3 )) with a P‐Au‐P environment. If the starting gold complex is [Au(C 6 F 5 )(tht)], reaction with the phosphine produces [Au(C 6 F 5 )(PPh 2 CH 2 SPh)] ( 6 ) from which, by reaction with AgCF 3 SO 3 or [Cu(CH 3 CN) 4 ]CF 3 SO 3 , the “snake”‐type linear complexes [Au 2 M(C 6 F 5 ) 2 (PPh 2 CH 2 SPh) 2 ]CF 3 SO 3 (M=Ag ( 7 ), Cu ( 8 )) are obtained. If the silver starting complex is AgCF 3 CO 2 , reaction in a 1:1 ratio gives the tetranuclear complex [Au 2 Ag 2 (C 6 F 5 ) 2 (PPh 2 CH 2 SPh) 2 (CF 3 CO 2 ) 2 ] ( 9 ). When the molar ratio is 1:2 the trinuclear complex [AuAg 2 (C 6 F 5 )(CF 3 CO 2 ) 2 (PPh 2 CH 2 SPh)] ( 10 ) is obtained. According to ab initio calculations, the presence of only one gold atom is enough to induce metallophilic attractions in the group congeners, and this effect can be modulated depending on the gold ligand.