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.

Heterometallic complexes with gold(I) metalloligands: self-assembly of helical dimers stabilized by weak intermolecular interactions and solvophobic effects.

New gold(I) alkynyl metalloligands bpylCCAuL, bpyl'CCAuPPh3 , and PPN[Au(CCbpyl')2 ] (bpyl or bpyl'=2,2'-bipyridin-5-yl or -4-yl, respectively; L=PMex Ph3-x (x=1-3), P(C6 H3 Me2 -3,5)3 , PCy3 , XyNC) have been synthesized. Ligands bpylCCH and metalloligands bpylCCAuL (L=PPh3 , PMePh2 , PCy3 , CNXy) react with MX2 (M=Fe, Zn, X=ClO4 ; M=Co, X=BF4 ) to give complexes [M(bpylCCZ)3 ]X2 (Z=H or AuL). In most cases, these complexes are mixtures of fac and mer isomers in a statistical distribution, in both CH2 Cl2 and MeCN. However, for L=PPh3 , the fac isomer is dominant in MeCN. NMR and ESI-MS studies, together with the crystal structure of [Co(bpylCCAuPPh3 )3 ](BF4 )2 , suggest that this solvent dependence is originated by the formation of helical dimers between two fac complexes in MeCN. These dimers are stabilized by solvophobic effects and multiple intermolecular interactions. Complex [Fe(Ph3 PAuCCbpdiylCCAuPPh3 )3 ](ClO4 )2 (bpdiyl=2,2'-bipyridin-5,5'-diyl) was obtained by reaction of three diauro diethynylbipyridines and Fe(ClO4 )2 .

Self-assembly of looped triple-stranded helicates.

The reaction of the organogold metallaligand [(AuC[triple bond]Cbpyl)(2)(mu-Ph(2)P(CH(2))(4)PPh(2))] (bpyl = 2,2'-bipyridin-5-yl) with Fe(2+) or Zn(2+) ions gave helicates where the three ligand strands adopt a unique looped geometry.