Bimetallic palladium(II) complexes containing classical NHC donor ligands are becoming increasingly popular owing to their various catalytic applications. However, examples of the aforementioned complexes with mixed NHC/PPh3 ligands are still rare. Bimetallic palladium(II) complexes possessing these mixed ligands are described starting from a C2‐symmetric bis‐imidazolium salt containing 4,4′‐substituted central biphenyl ring. All the palladium(II) complexes have been tested as precatalysts in α‐arylation of oxindole and Suzuki–Miyaura coupling reactions. The complex composed of mixed NHC/PPh3 donor ligands shows superior catalytic activity compared with the corresponding PEPPSI type complexes when applied in α‐arylation of oxindole. The dinuclear complexes display better activity compared with the mononuclear complexes. The preliminary electrochemical measurements show the facile oxidation of PdII in the presence of combined NHC/PPh3 ligands compared with a combination of NHC/Py ligands.

The field of asymmetric catalysis is rapidly developing and the chiral ligands play a key role in enantioselective transition‐metal catalysis. The electron‐rich chiral N‐heterocyclic carbenes (NHCs) have established themselves as a popular class of stereodirecting ancillary ligands to catalyze enantioselective organic transformations in more efficient ways. Several novel transition‐metal complexes in combination with tailored ligand design have emerged during last few decades in asymmetric catalysis. The tailor‐made NHCs can easily be accessed due to the modular synthesis of their parent azolium salt precursors. Their donor capability and the molecular shape can easily be tuned by changing substituent at N‐atom or by changing the cyclic backbone framework. This review article aims to describe the recent advances in this rapidly evolving research area of enantioselective catalysis using well‐defined transition‐metal complexes possessing chiral NHC donor ligands.

Heterobimetallic complexes featuring mesoionic carbene (MIC) donor ligands are gaining enormous popularity in tandem catalysis owing to the combined action of two different metal centers during catalysis. A rare version...

A new C 3 -symmetric tris-imidazolium tribromide salt 3, featuring 1,3,5-substituted triethynylbenzene, was used for the preparation of a trinuclear Pd II pyridine-enhanced precatalyst preparation stabilization and initiation-type (PEP-PSI) complex by triple C2 deprotonation followed by the addition of PdCl 2 . Trinuclear Pd II complex possessing a combination of NHC and PPh 3 ligands has also been synthesized. The corresponding mononuclear palladium(II) complexes have also been synthesized for the comparison purpose. All these complexes have been characterized by using NMR spectroscopy and ESI mass spectrometry. The molecular structure of the trinuclear palladium(II) complex bearing mixed carbene and pyridine donor ligands has been established by using single crystal XRD. All the palladium(II) complexes have been used as pre-catalysts, which gave good to excellent yields in intermolecular α-arylation of 1-methyl-2oxindole and Sonogashira coupling reaction. Catalytic studies indicate an enhanced activity of the trinuclear Pd II complex in comparison to the corresponding mononuclear Pd II complex for both catalytic transformations. The better performance of the trinuclear complex has also been further supported by preliminary electrochemical measurements. A negative mercury poison test was observed for both the aforementioned catalyses and therefore, it is likely that these organic transformations proceed homogeneously.