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

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.

[1]  P Pulay,et al.  Local Treatment of Electron Correlation , 1993 .

[2]  D. Sundholm,et al.  Luminescent Characterization of Solution Oligomerization Process Mediated Gold−Gold Interactions. DFT Calculations on [Au2Ag2R4L2]n Moieties , 2000 .

[3]  A. Lledós,et al.  Theoretical Study on the Origin of Enantioselectivity in the Bis(dihydroquinidine)-3,6-pyridazine·Osmium Tetroxide-Catalyzed Dihydroxylation of Styrene , 1999 .

[4]  G. Sheldrick,et al.  Synthesis and reactivity of bimetallic Au–Ag complexes. X-Ray structure of a chain polymer containing the moiety…(F5C6)2Au(µ-AgSC4H8)2Au(C6F5)2… , 1981 .

[5]  Pekka Pyykkö,et al.  Theory of the d10–d10 Closed‐Shell Attraction: 1. Dimers Near Equilibrium , 1997 .

[6]  Mariano Laguna,et al.  Synthesis and reactivity of bimetallic Au–Ag polyfluorophenyl complexes; crystal and molecular structures of [{AuAg(C6F5)2(SC4H8)}n] and [{AuAg(C6F5)2(C6H6)}n] , 1984 .

[7]  N. Runeberg,et al.  Experimental and theoretical studies of the d8-d10 interaction between Pd(II) and Au(I): bis(chloro[(phenylthiomethyl)diphenylphosphine]gold(I))- dichloropalladium(II) and related systems. , 2000, Inorganic chemistry.

[8]  T. H. Dunning Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[9]  John P. Campbell,et al.  Single-Crystal X-ray Structure of the Cation Radical of 3‘,4‘-Dibutyl-2,5‘‘-diphenyl-2,2‘:5‘,2‘‘-terthiophene: Definitive Evidence for π-Stacked Oxidized Oligothiophenes , 1996 .

[10]  John P. Campbell,et al.  From Monomers to π-Stacks. A Comprehensive Study of the Structure and Properties of Monomeric, π-Dimerized, and π-Stacked Forms of the Cation Radical of 3‘,4‘-Dibutyl-2,5‘‘-diphenyl-2,2‘:5‘,2‘‘-terthiophene , 1997 .

[11]  Rodríguez,et al.  Heteropolynuclear complexes with the ligand Ph2PCH2SPh: theoretical evidence for metallophilic Au-M attractions , 2000, Chemistry.

[12]  M. Schütz,et al.  The aurophilic attraction as interpreted by local correlation methods , 1999 .

[13]  P. Pyykkö,et al.  Ab initio Calculations on the (ClAuPH3)2 Dimer with Relativistic Pseudopotential: Is the “Aurophilic Attraction” a Correlation Effect? , 1991 .

[14]  H. Stoll,et al.  Energy-adjustedab initio pseudopotentials for the second and third row transition elements , 1990 .

[15]  F. Scherbaum,et al.  “Aurophilicity” as a Consequence of Relativistic Effects: The Hexakis(triphenylphosphaneaurio)methane Dication [(Ph3PAu)6C]2⊕ , 1988 .

[16]  Peter Pulay,et al.  Localizability of dynamic electron correlation , 1983 .

[17]  Hans-Joachim Werner,et al.  Local treatment of electron correlation in coupled cluster theory , 1996 .

[18]  William L. Jorgensen,et al.  Aromatic-aromatic interactions: free energy profiles for the benzene dimer in water, chloroform, and liquid benzene , 1990 .

[19]  T. Tamm,et al.  Theory of the d10−d10 Closed-Shell Attraction. 4. X(AuL)nm+ Centered Systems , 1998 .

[20]  D. Sundholm,et al.  INTERMOLECULAR INTERACTIONS IN P-CHLOROBENZOIC ACID DIMERS , 1998 .

[21]  K. Nakamoto Infrared and Raman Spectra of Inorganic and Coordination Compounds , 1978 .

[22]  Paul G. Mezey,et al.  A fast intrinsic localization procedure applicable for ab initio and semiempirical linear combination of atomic orbital wave functions , 1989 .