A Study of the Interactions in an Extended Unsupported Gold-Silver Chain

Abstract

The complex [Ag(Py)3][Au(C6F5)2]·Py (1) (Py = pyridine) has been prepared by the reaction of NBu4[Au(C6F5)2] with AgClO4 in the presence of pyridine. The crystallographic measurements indicate the presence of an extended unsupported one‐dimensional chain of alternating gold and silver atoms. This arrangement is due to the formation of molecular Au−Ag ion pairs, to the π‐stacking of C6F5 and pyridine arene ligands and to the packing effects that lead to molecular ion pairs at short distance. Theoretical calculations based on approximate experimental distances and angles reveal the presence of both metallophilic AuI−AgI and aromatic C6F5‐pyridine interactions. From a theoretical point of view the nature of the intermetallic attraction arises from both an ionic contribution and from dispersion‐type correlation effects; the aromatic interaction is mainly due to dispersion‐type correlation effects.

Silver Compounds in Synthetic Chemistry. 1 A Facile Preparative Route for Pentafluorophenylsilver, AgC 6 F 5 and its Use as an Oxidative Pentafluorophenyl Group Transfer Reagent in Reactions with Group 12 to 16 Elements — the Single Crystal Structure of AgC 6 F 5 · EtCN, the First Arylsilver Derivative Crystallising in Infinite Chains

“…Hence, AgC 6 F 5 · EtCN is the first example exhibiting an infinite chain. On the other hand a similar arrangement was found for the mixed silver gold compound [Ag(C 5 H 5 N) 3 ][Au(C 6 F 5 ) 2 ] · C 5 H 5 N [23].…”

Luminescent Gold(I) and Silver(I) Complexes of 2-(Diphenylphosphino)-1-methylimidazole (dpim): Characterization of a Three-Coordinate Au(I)−Ag(I) Dimer with a Short Metal−Metal Separation

“…The two silver atoms are bridged by two dpim ligands in a head to tail fashion. Each silver is three coordinate, bound to a phosphorus atom of one ligand, an imine nitrogen of the second ligand, and to an acetonitrile (19), and 115.38 (16)°respectively. The Ag-Ag separation is 2.9932-(9) Å.…”

Perfluoroarylgold complexes

“…(25) is carried out in dichloromethane in the presence of excess pyridine, a colorless solid of stoichiometry [AuAg(C 6 F 5 ) 2 (py) 4 ] is obtained [167]. The single-crystal X-ray diffraction study of this species shows the silver atom distorted over two positions (50% each one), which does not enable a valid analysis of its bond distances and angles.…”

“…This arrangement is the result of the formation of molecular Au-Ag ion pairs, to the -stacking interactions between C 6 F 5 and pyridine arene ligands and to packing effects. Moreover, theoretical calculations based on approximate distances and angles have been carried out, revealing the presence of both metallophilic Au I · · ·Ag I and aromatic C 6 F 5 -py interactions [167].…”