Three types of hybrid phosphorus-imidazolium salts, 1-methyl-3-(3-((diphenylphosphino)methyl)benzyl)-1H-imidazol-3-ium hexafluorophosphate (2.PF6), 1-methyl-3-(3(di-tert-butylphosphinooxy)phenyl)imidazolium iodide (8a), and 3-(3-((diphenylphosphoryl)methyl)phenyl)-1-methyl-1H-imidazol-3-ium iodide (11) have been prepared and used as precursor; to phosphine-NHC phosphinite-NHC, and phosphoryl-NHC metal complexes, respectively. The structure of 11 has been determined by X-ray diffraction. The A g (I) and Ir(I) complexes of the phosphine-NHC [Ag(mu-P-NHC,kappa C,kappa P)](PF6)(2) (3) and [Ir(cod)(mu - P - NHC,kappa C,kappa P)](2)(PF6)(2) (4), were obtained and characterized by NMR, ESI-MS, elemental analysis, and X-ray diffraction. Both complexes are dinuclear and dicationic, with two P-NHC ligands bridging the two metal centers. The presence of the P donor led for 3 to an unprecedented structure compared to that of related Ag(I) complexes with trans spanning bis-NHC ligands. Complex 4 is the first example of a dinuclear iridium complex with a hybrid P-NHC ligand. The new hydrido, Ir(III) pincer-type complex [IrH(CNHCCCNHC)(MeCN)]PF6 (7) is suggested to have a square-pyramidal structure. The tetranuclear Ag(I) complex With the phosphinite-NI-IC ligand, [Ag-2(mu(3)-I)(mu-PO-NHC,kappa P,kappa C-NHC)](2) (9a) has a cubane-type structure, with alternating silver and iodine apexes and two PO-NHC ligands bridging opposite edges of the Ag-4 tetrahedron. The Ir(III) pincer complexes [IrH(I)(PO-NHC,kappa P,kappa C,kappa C-NHC)(Me)] (10a) and [IrH(I)(PO-NHC,kappa P,kappa C,kappa C-NHC)(n-Bu)] (10b), with Me or n-Bu substituents on the nitrogen atom, respectively, have been prepared and characterized. Ag(I) and Cu(I) complexes with the Phosphoryl-NHC ligand are reported and the centrosymmetric structure of the latter, [Cu(OP-NHC,kappa C) (14 I){C ( I)}] (13), was established by X-ray diffraction and consists of a central Cu-2(mu-I)2 rhombus connected by single iodide bridges to two Cu(OP-NHC,kappa C-NHC)(2) moieties. The Ir(III) hydride pincer complexes 10a,b were tested as catalyst precursors for the C H bond activation of alkanes. Although their efficiency was significantly lower for transfer dehydrogenation from cyclooctane (coa) to t-butylethyle n (tb) than that of known PCP-Ir systems, these results represent the first attempts to study the catalytic properties of hybridPe:NHeC iridium pincer complexes.