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  • Title: Preparation of Au(I), Ag(I), and Pd(II) N-heterocyclic carbene complexes utilizing a methylpyridyl-substituted NHC ligand. formation of a luminescent coordination polymer.
    Author: Catalano VJ, Etogo AO.
    Journal: Inorg Chem; 2007 Jul 09; 46(14):5608-15. PubMed ID: 17547393.
    Abstract:
    Reaction of the imidazolium N-heterocyclic carbene precursor containing a methyl-substituted pyridyl functionality [HCH3im(CH3py)]PF6, 1, with Ag2O produces the homoleptic Ag(I) complex, [Ag(CH3im(CH3py))2]PF6, 2. In a simple carbene transfer reaction the analogous Au(I) species, [Au(CH3im(CH3py))2]PF6, 3, is formed by treatment of 2 with Au(tht)Cl in dichloromethane. Both 2 and 3 are structurally similar with nearly linearly coordinated NHC ligands. The methyl group appended to the pyridyl ring inhibits rotation of the pyridyl group at room temperature. Addition of AgBF4 to a hot propionitrile solution of 3 followed by crystallization with diethyl ether yields the one-dimensional coordination polymer, {[AuAg(CH3im(CH3py))2(NCCH2CH3)](BF4)2}n, 4, which contains Au-Ag separations of 2.9845(5) and 2.9641(5) A with intermetallic angles of 167.642(14) degrees and 162.081(9) degrees. This material is intensely luminescent in the solid state and exhibits an emission band at 453 nm (lambdaex=350 nm). Nearly colorless [Pd(CH3im(CH3py))2Cl]PF6, 5, is produced upon treatment of 2 with PdCl2(NCC6H5)2. The Pd(II) center in 5 is coordinated to one NHC ligand in a chelate fashion, while the second NHC is bound solely through the carbon center. The X-ray crystal structures of 1-5 are reported.
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