62827-82-1Relevant articles and documents
Multidentate N-Heterocyclic Carbene Complexes of Nickel and Palladium: Structural Analysis and Catalytic Application in Mizoroki–Heck Coupling Reaction
Liu, Li-Cheng,Tzeng, Yan-Hsiang,Hung, Cheng-Hau,Lee, Hon Man
, p. 3601 - 3611 (2020/09/01)
Two series of electron-rich metal (Ni and Pd) complexes, namely a pyridine-coordinated tridentate NHC/amidate/phenoxy metal complex and a tetradentate complex bearing an extra pyridyl group, were synthesized. Two carbene moieties, imidazole-based and benzimidazole-based NHCs, were also incorporated into the ligand backbones. Seven of the new complexes were structurally characterized and comparative structural analysis revealed that the tetradentate complex with a flanking pyridyl side-arm was less distorted, leading to chelation-assisted stronger NHC coordination and hence a shorter metal–carbene bond. The catalytic activities of the two sets of palladium complexes for the Mizoroki–Heck coupling reaction were investigated. The comparative data showed that despite the higher thermal stability and the presence of the flanking hemilabile pyridyl side-arm which provided unsaturation to the metal center, the catalytic performance was slightly inferior to that of the tridentate palladium complex with a “throw-away” pyridine ligand. The tridentate palladium complex with the benzimidazole-based NHC moiety was the most effective catalyst, allowing the utilization of a range of aryl chlorides including deactivated substrates with a low 0.2 mol-% Pd loading in molten n-tetrabutylammonium bromide.
Postmodification Approach to Charge-Tagged 1,2,4-Triazole-Derived NHC Palladium(II) Complexes and Their Applications
Nguyen, Van Ha,Ibrahim, Mansur B.,Mansour, Waseem W.,El Ali, Bassam M.,Huynh, Han Vinh
, p. 2345 - 2353 (2017/06/30)
Charge-tagged bis(1,2,4-triazolin-5-ylidene)palladium(II) complexes have been successfully synthesized via a postmodification strategy. Reacting PdBr2 with bromo-functionalized 1,2,4-triazolium salts A·HBr and B·HBr in the presence of silver oxide afforded the bis(carbene)palladium(II) complexes trans-[PdBr2(A)2] (1a) and trans-[PdBr2(B)2] (1b), which contain tethered bromoalkyl chains. Subsequent postcoordinative nucleophilic substitution converted the bromo into ammonium groups, producing the water-soluble complexes trans-[PdBr2(C)2]Br2 (2a) and trans-[PdBr2(D)2]Br2 (2b), while attempts to prepare ammonium-functionalized triazolium salts for direct metalation were futile. All four complexes were fully characterized by means of multinuclear NMR spectroscopy, ESI mass spectrometry, elemental analysis, and X-ray diffraction analysis. The presence of trans-anti and trans-syn rotameric complexes in solution was elucidated by 1H and 13C NMR spectroscopy and theoretical calculations. Additionally, the two charge-tagged complexes, 2a,b, were found to be highly active precatalysts for the Suzuki-Miyaura and Mizoroki-Heck reactions in iPrOH/H2O and molten TBAB as an ionic liquid.