New indenylidene-type metathesis catalysts bearing unsymmetrical N-heterocyclic ligands with mesityl and nitrobenzyl substituents

ABSTRACT: New indenylidene-type second generation catalysts bearing modified unsymmetrically substituted N-heterocyclic carbene ligands were synthesized. The complexes contain an N-mesityl and N′-nitrobenzyl substituted NHC ligand. The precursors of free carbenes—imidazolinium salts—were obtained in an easy and environment-friendly way (under aqueous or neat conditions). The new catalysts were prepared by reaction of in situ generated carbenes with a 1st generation indenylidene catalyst, containing pyridine ligands instead of tricyclohexylphosphine. The complexes were tested in RCM, CM, and ene-yne metathesis model reactions in commercial-grade solvents in air. Their activities were compared with that of commercially available indenylidene catalyst. The structures of complexes and their stability were investigated using static DFT calculations with mixed basis set. GRAPHICAL ABSTRACT: [Image: see text] ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s00706-016-1697-7) contains supplementary material, which is available to authorized users.