Phenylene- and Biphenylene-Bridged Bis-Imidazolylidenes of Palladium. Influence of the Presence of Pyrene Tags on the Catalytic Activity of the Complexes

Abstract

A series of dimetallic complexes with N-heterocyclic carbene ligands with formally identical stereoelectronic properties have been obtained and fully characterized. The dimetallic complexes were bridged by bis-imidazolylidenes, with different spacers (phenylene and biphenylene). The N substituents were methyl or methylpyrene groups. The related monometallic complexes were also obtained. The catalytic properties of the complexes were tested in the acylation of aryl halides with hydrocinnamaldehyde and in the Suzuki–Miyaura coupling between aryl halides and arylboronic acids. In general, the dimetallic complexes display better activities than the monometallic analogues. The results also indicate that those complexes with pyrene groups at the N substituents display better catalytic activities than those with N-methyl groups. These observations are interpreted as a consequence of the π stacking interaction between the substrates and the pyrene groups in the pyrene-containing catalysts, which may provide some beneficial catalytic properties. The addition of a catalytic amount of pyrene to the Suzuki–Miyaura coupling reactions results in a partial inhibition of the activities of the complexes with the pyrene substituents, while the activity of the complexes with the N-methyl groups is not affected.