Aryl Grignard cross-coupling of aryl chlorides catalysed by new, highly active phosphine/imidazolium nickel(II) complexes

Two new zwitterionic nickel(II) complexes, bearing phosphine/imidazolium ligands, have been prepared. Their catalytic activity, and the activity of an analogous Ni(II) complex, previously described by us, has been evaluated with a range of aryl chlorides, an aryl bromide and arylmagnesium halides. The catalytic activity is related to the length of the tether between the carbene and phosphine moieties. Thus the catalysts possessing a six-membered metallacycle are more active than that having a seven-membered metallacycle. Changing from a mesityl (Mes) to a 2,6-diisopropylphenyl (DIP) on the imidazole ring does not strongly influence the activity. The three complexes show moderate to very good activities with most substrates, and enhanced selectivities compared to previously published Ni(II)/N-heterocyclic carbene systems. The low activity observed with 4-chlorobenzotrifluoride seems to be related to the presence of a phosphine on the ligands.

Graphical abstractThree zwitterionic nickel(II) complexes, bearing phosphine/imidazolium ligands, have been prepared and characterised. Their catalytic activity has been evaluated with a range of aryl chlorides and arylmagnesium halides. They have shown moderate to very high activities with most substrates, and very good selectivities in favour of the heterocoupling products. Figure optionsDownload full-size imageDownload as PowerPoint slide