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Platinum complexes featuring pyridine bis-N-heterocyclic-imidazol-2-ylidene/-mesoionic-triazol-5-ylidene donors as pincer ligands and chloro (-Cl), acetonitrile (-NCCH3) or cyano (-CN) groups as auxiliary ligands are prepared as highly strained organometallic phosphors. X-ray structures of four of these complexes confirm a distorted square planar geometry, where the pincer ligand and its mesityl wingtips occur in a twisted conformation to each other. Electrochemical and photophysical characterization have been carried out and the experimental results are interpreted with the aid of density functional theory calculations. Emission responses of complexes under exposure to different vapors and mechanical shear are reported. Notably, the platinum complex featuring pyridine bis-imidazol-2-ylidene and a weakly donating acetonitrile auxiliary ligand exhibited strong aquachromic and mechanochromic emission responses, showing color changes from sky blue to green or yellow-green.

Homoleptic ruthenium complexes [Ru(Ln)2]2+ bearing unsymmetric pyridine-based bis N-heterocyclic carbene (NHC) pincer ligands are synthesized and structurally characterized. These complexes feature the coexistence of a five-membered and a six-membered ruthenacycle within the same ligand framework, allowing an ideally octahedral CNHC–Ru–NPy bite angle close to 90°. In the solid state, impressive 3MLCT lifetimes of microsecond regime were detected in all of the complexes, of which [Ru(L4)2]2+, featuring four benzimidazol-2-ylidene donors, exhibited the longest values. Electronic properties of all of the ruthenium complexes are investigated by cyclic voltammetry and spectroscopic techniques. Density functional theory results were used to support the experimental observations.

Ru(II) complexes with two chelating di-N-heterocyclic carbenes (NHC) and two acetonitrile ligands (NHC = 1,1′-dialkyl-3,3′-methylene-diimidazol-2,2′-diylidene, and alkyl = methyl and n-butyl) were synthesized and structurally characterized. The crystal structures of the complexes determined by X-ray diffraction analyses show that the Ru(II) center is bound to two bidentate carbene ligands and two acetonitrile molecules, forming a distorted octahedron. The complexes prove to be an efficient catalyst having exceedingly high turnover frequencies and good reusability in transfer hydrogenation of ketones.

Homoleptic Pd(II) complexes with one and two chelating di-N-heterocyclic carbene (NHC) ligands tagged with pyridinium cation, [Pd2(PyBuCCme)2Cl2](PF6)6 and [Pd (PyBuCCme)2](PF6)6 (PyBuCCme = 1,1′-di-N-(2-pyridinium)butyl-3,3′-methylenediimidazol-2,2′-diylidene), were synthesized and their square planar molecular geometry were determined by X-ray diffraction analysis. These complexes exhibited high catalytic activity toward Heck reaction in both DMF and water.

N-Pyridyl, N'-amido functionalized imidazolium bromides were obtained in high yields as an N-heterocyclic carbene (NHC) precursor and used as bidentate or a pincer ligands to obtain ruthenium complexes via a silver NHC transmetallation route. The incorporation of a phenyl group as an amido-N substituent (R = Ph) results in a bidentate coordination mode through the C(NHC) and N(pyridyl) donors, whereas in its absence (R = H) a pincer coordination mode was observed through the N(pyridyl)^C(NHC)^O(amido) donors. The ruthenium complex featuring a pincer type NCO coordination mode with a protic NH function adjacent to the coordinating O(amido) atom was found to efficiently catalyse the oxidation of activated alcohols effecting quantitative conversions within 30 minutes. However the oxidation of deactivated alcohols required longer reaction times to effect the quantitative transformation.

A new series of ruthenium(II) carbonyl complexes with benzene-based CCC-pincer bis-(carbene) ligands, [((R)CCC(R))Ru(CO)2(X)](0/+) and [((R)CCC(R))Ru(CO)(NN)](+) ((R)CCC(R) = 2,6-bis-(1-alkylimidazolylidene)benzene, R = Me or (n)Bu; X = I, Br, CH3CN, or 6-(aminomethyl)pyridine (ampy); NN = 2·CH3CN, or chelating ampy or bipyridine), was synthesized and fully characterized. X-Ray structure determinations revealed that these eight complexes have pseudo-octahedral configurations around the ruthenium center with the pincer ligand occupying three meridional sites. These complexes prove to be efficient precatalysts demonstrating very good activity and reusability for the transfer hydrogenation of ketones.

A novel palladium complex with chelating NHC ligand is prepared and efficiently applied as a reusable catalyst for the Heck reaction.