Electronic effects in mixed N-heterocyclic carbene/phosphite indenylidene ruthenium metathesis catalysts.

Five new complexes [RuCl(SIMes)(Ind)(O-pXCH)] bearing different para-substituted triphenylphosphites (X = H, OCH, CF, Cl, SF and CN) were synthesised and used to study the effect of the electronic properties of the phosphite on olefin metathesis activity. Investigations of the physical properties of the new ligands and complexes were performed using physicochemical and DFT calculations. The catalytic activity of the complexes was benchmarked in challenging ring closing metathesis transformations featuring the formation of tetra-substituted double bonds.

Generalization of the Copper to Late-Transition-Metal Transmetallation to Carbenes beyond N-Heterocyclic Carbenes.

Carbene transition-metal complexes have become a prevalent family of catalysts enabling numerous organic transformations. Their facile synthetic access is a matter of great importance. To this end, the Cu(I) -NHC transfer methodology has emerged as a powerful alternative presenting attractive advantages over other methods.

A simple access to transition metal cyclopropenylidene complexes.

We report the first example of BAC-Cu complex (BAC = bis(diisopropylamino)cyclopropenylidene) and its use as a carbene-transfer reagent, allowing access to Au-, Pd-, Ir- and Rh-BAC compounds. Catalytic experiments show the high activity of the [CuCl(BAC)] complex in Click chemistry.