A palladium(0) NHC complex Pd0(LH1)2(MA) (MA = maleic anhydride) was prepared from the amide-imidazolium salt [LH1H2]Cl (H1 = NH proton; H2 NCHN proton). The X-ray diffraction studies confirmed that a η2-MA ligand and two monodentate NHC ligands with the H1 protons remaining intact are coordinated. These NH protons are involved in intra- or intermolecular hydrogen bonds stabilizing the solid-state structure. Degradation of Pd(LH1)2(MA) in air leads to the formation of the chelate complex trans-PdIIL2 and other unidentified products. Negative-ion electrospray mass spectrometry revealed some intriguing Pd(0) species, including a 14-electron [Pd0L]− species that bears only a bidentate NHC/amido ligand. The anionic amido group imparts a high electron density on a palladium center, as shown by X-ray photoelectron study. The palladium(0) precatalyst is highly efficient in catalyzing Heck reactions with activated aryl chlorides in ionic liquid. For deactivating aryl chlorides and bulky aryl bromides, cis-PdIIL2 is more effective. A range of Heck-coupled products can be prepared by Pd0(LH1)2(MA) and cis-PdIIL2. The latter complex also successfully mediates one-pot sequential Heck/Heck and Suzuki/Heck coupling reactions with 4-bromochlorobenzene as substrate.

Five new three-dimensional transition metal coordination polymers (CPs) with dia and different aromatic carboxylates, [Cd(oba)(dia)0.5] (1), [Cd(Hbtc)(dia)]·3H2O (2), and [M3(2-stp)2(dia)6(H2O)2] (3a, M = Cd; 3b, M = Co; 3c, M = Ni) were synthesized under hydrothermal condition (dia = 9,10-di(1H-imidazol-1-yl)anthracene; oba = 4,4′-oxybis(benzoate); btc = benzene-1,3,5-tricarboxylate; 2-stp = 2-sulfoterephthalate). Compounds 3a–c are isostructural. The coordination geometries at cadmium in 1, 2, and 3a are capped trigonal prism, pentagonal bipyramid, and octahedron, respectively. This diversity in coordination geometry is in sharp contrast to 3c and previously reported nickel complexes of a similar ligand set. The difference in metal-containing node geometries and carboxylate structures results in diverse network connectivity, including a tcs topology for 1, an unprecedented binodal topology of (42.63.85)(42.6) for 2, and a rare trinodal topology of (4.64.8)2(43.63)2(44.610.8) for 3. Based on secondary building units, the networks in 2 and 3 can be, alternatively, described as rob and pcu (or ilc) nets, respectively. This work shows the effect of the specific ion and the rich potential of using bulky bis(imidazole) and aromatic carboxylate as ligands in the construction of CPs with unusual topologies.