Assembly of Heterometallic Rigid-Rod Complexes and Coordination Oligomers from Gold(I) Metalloligands

The
reactions of TpylC6­H4CCAuL
(Tpyl = 2,2′:6′,2″-terpyridin-4′-yl; L
= PPh3, CNXy; Xy = 2,6-dimethylphenyl) with MX2·nH2O (M = Fe, X = ClO4; M = Co, X = BF4; M = Zn, X = TfO, ClO4) in
a 2:1 molar ratio give complexes [M­(Tpyl­C6H4­CC­AuL)2]­X2. Similarly,
the reactions of PPN­[(TpylC6H4­CC)2Au] (PPN = (Ph3P)2N) with an equimolar
amount of MX2·nH2O give
coordination oligomers [M­{(TpylC6H4­CC)2­Au}]nXn (M = Fe, Zn, X = ClO4; M = Co, X = BF4). The complexes and oligomers have been isolated and characterized.
The crystal structures of [Fe­(Tpyl­C6H4­CC­AuCNXy)2]­(ClO4)2 and [Co­(Tpyl­C6H4­CC­AuPPh3)2]­(BF4)2 have been
determined by X-ray diffraction. The hydrodynamic sizes of complexes
[M­(Tpyl­C6H4­CC­AuPPh3)2]­X2 and coordination oligomers
[M­{(Tpyl­C6H4­CC)2­Au}]nXn have been studied by NMR diffusion spectroscopy and dynamic light
scattering measurements.