Mesitylgold(I) and Silver(I) Perfluorocarboxylates as Precursors of Supramolecular Au/Ag Systems
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- 作者：Eduardo J. Ferná ; ndez ; Antonio Laguna ; José ; M. Ló ; pez-de-Luzuriaga ; M. Montiel ; M. Elena Olmos ; Javier Pé ; rez ; Raquel C. Puelles
- 刊名：Organometallics
- 出版年：2006
- 出版时间：August 28, 2006
- 年：2006
- 卷：25
- 期：18
- 页码：4307 - 4315
- 全文大小：316K
- 年卷期：v.25,no.18(August 28, 2006)
- ISSN：1520-6041
文摘
Reaction of [Ag(CF3CO2)] with tetrahydrothiophene (tht) (2:1) in dichloromethane leads to the synthesisof [Ag4(CF3CO2)4(tht)2] (1), which further reacts with mesitylgold(I) ([Au(mes)]) (1:1) to afford[AuAg4(mes)(CF3CO2)4(tht)]n (3). Treatment of [Au(mes)] with [Ag(RCO2)] (R = CF3, CF2CF3) and tht(molar ratio 1:4:1 or 1:4:3) leads to the new Au/Ag systems [AuAg4(mes)(RCO2)4(tht)x]n (x = 1, R =CF3 (3), CF2CF3 (4); x = 3, R = CF3 (5), CF2CF3 (6)). The crystal structures of 3, 4, and 6 have beenestablished by X-ray diffraction, all of them displaying Au···Ag interactions supported by mesityl ligandsthat bridge three metal centers in an unprecedented situation in transition metal chemistry. AdditionalAu-S-Ag and Ag-O-Ag (3 and 4) or Ag-S-Ag (6) bonds result in two-dimensional polymers thatcontain both Au···Ag and Ag···Ag contacts. Treatment of 3 with water (1:2) in dichloromethane leadsto {[AuAg4(mes)(CF3CO2)4(tht)(H2O)]·H2O·CH2Cl2}n (7), whose crystal structure shows the partial breakof the cyclic [Ag2(
-RCO2)2] dimer present in the structures of 3, 4, and 6, probably caused by thecoordination of one molecule of water to one of the AgI centers. It also displays Au···Ag and Ag···Aginteractions, as well as Ag-C bonding interactions and additional Ag-O contacts, which result in amonodimensional polymer. The crystal structure of 1 has also been determined by X-ray diffraction.
-RCO2)2] dimer present in the structures of 3, 4, and 6, probably caused by thecoordination of one molecule of water to one of the AgI centers. It also displays Au···Ag and Ag···Aginteractions, as well as Ag-C bonding interactions and additional Ag-O contacts, which result in amonodimensional polymer. The crystal structure of 1 has also been determined by X-ray diffraction.