posted on 2016-01-26, 12:06authored byDan Yuan, Han Vinh Huynh
A series
of Pd(II) dibromido complexes 2–6 bearing cis-chelating hetero-dicarbenes, which
contain two different types of NHCs linked by a propylene chain, have
been synthesized. In most cases, the N-methylbenzimidazolin-2-ylidene
moiety was kept as one NHC donor, while the other one varies with
different heterocyclic backbones. As an exception, the hetero-diNHC
in complex 8 is derived by combining 1,2,4-triazole and
indazole precursors instead. Analogous complexes 9–17, carrying more labile CF3CO2– or CH3CN ligands, were synthesized by reacting
the aforementioned bromido complexes with AgO2CCF3 or AgOTf in CH3CN. A systematic catalytic comparison
of 9–17 in the direct arylation of
pentafluorobenzene with 4-chlorobromobenzene was carried out, and
complexes that contain bulkier and less electron-donating ligands
were found to be more active. Complex 12, carrying the
mesitylimidazolin-2-ylidene unit, proved to be the most efficient,
and its activity was also tested in the direct arylation of tetrafluorobenzenes.