The gold(I) complex [Au3(C6F5)3(eta3-Fcterpy)](Fcterpy = 4'-ferrocenyl-2,2'ratio6',2''-terpyridine) represents the first example of a terpyridine ligand bonded to three different metals. The aurophilic interactions present in the molecule may contribute to the overall stability of the system, as was shown by DFT calculations. The positive Mayer indices (0.152 and 0.138), as well as the magnitude of the binding interaction between terpy and the Au(I)L fragments, support this interpretation.

The reaction of the unsymmetrical ligands 1-diphenylphosphino-1'-(phenylsulfanyl)ferrocene and 1-diphenylphosphino-1'-(phenylselenyl)ferrocene, Fc(EPh)PPh2(E = S, Se), with several group 11 metal derivatives leads to the synthesis of complexes of the type [MX{Fc(EPh)PPh2}](M = Au, X = Cl, C6F5; M = Ag, X = OTf), (OTf = trifluoromethanesulfonate), [M{Fc(EPh)PPh2}2]X (M = Au, X = ClO4; M = Ag, X = OTf), [M(PPh3){Fc(EPh)PPh2}]OTf (M = Au, Ag), [Au2{Fc(SPh)PPh2}2](ClO4)2, [Au(C6F5)2{Fc(SePh)PPh2}]ClO4, [Au(C6F5)3{Fc(EPh)PPh2}], [Au2(C6F5)6{Fc(SePh)PPh2}] or [Cu{Fc(EPh)PPh2}2]PF6(E = S, Se). In these complexes coordination depends upon the metal centre; with gold it takes place predominantly to the phosphorus atom and with silver and copper to both phosphorus and chalcogen atoms. The treatment of some of the gold complexes with other metal centres affords heterometallic derivatives that in some cases are in equilibrium with the homometallic derivatives. Several compounds have been characterized by X-ray diffraction, four pairs of homologous compounds, yet not a single pair is isotypic. In many of them a three dimensional network is formed through secondary bonds such as hydrogen bonds, Au...Cl or Au...Se interactions. The complex [Ag(OTf){Fc(SePh)PPh2}] forms one-dimensional chains through trifluoromethanesulfonate bridging ligands.

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4Ј,4ЈЈЈ-Bis(ferrocenyl)-2,2Ј:6Ј,2ЈЈ:6ЈЈ,2ЈЈЈ:6ЈЈЈ,2ЈЈЈЈ-quinquepyridine (Fc 2 qpy) reacts with AgOTf (OTf = trifluoromethylsulfonate) to give a complex of stoichiometry [Ag(Fc2qpy)]-OTf. The crystal structure reveals a dinuclear arrangement among the cations with an Ag···Ag close contact of 3.089(2) Å . The ligands are wrapped around the silver atoms in a double helical array. Further hydrogen bonding between triflate units and the protons of the ferrocene or pyridine moieties results in a supramolecular structure. Theoretical stud-

The ligands {[bis(2‐pyridyl)amino]carbonyl}ferrocene (L1) and 1,1′‐bis{[bis(2‐pyridyl)amino]carbonyl}ferrocene (L2) have been prepared by treatment of the mono‐ or 1,1′‐bis(chlorocarbonyl)ferrocene derivatives with dipyridylamine in a 1:1 or 1:2 ratio, respectively. The ligand properties of these compounds towards group 11 and palladium complexes have been studied. Ligand L1 coordinates to these compounds to give four‐coordinate [Cu(L1)2]+, [PdCl2(L1)] and [Ag(OTf)(L1)(PR3)] or three‐coordinate [Ag(OTf)(L1)] and [Au(C6F5)(L1)] compounds. The ligand coordinates in a chelate fashion in all cases. The reactivity of L2 is somewhat different because coordination to copper or silver atoms can take place through several pyridine units either from different cyclopentadienido rings, as in [Cu(L2)]+, [Ag2(OTf)2(L2)] and [Ag(OTf)(L2)(PPh3)], or from the same cyclopentadienido ring, as in [Ag2(OTf)2(L2)(PPh3)2]. Coordination as a bridging ligand for four gold atoms has also been achieved in [Au4(C6F5)4(L2)] and [Au4(L2)(PPh3)4](OTf)4. The ligands and some complexes have been characterized by X‐ray diffraction studies and show the presence of several hydrogen bonds that lead to supramolecular structures.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)