Catalytic SNAr of unactivated aryl chlorides.

We present nucleophilic aromatic substitution of unsubstituted aryl chlorides via a mechanism that is catalytic in [CpRu(p-cymene)]PF6 and involves a Ru(η(6)-arylchloride) intermediate. From the spectroscopic evidence we infer that arene exchange is the rate limiting step in this process and develop several new Ru(ii) complexes that lower the activation barrier to arene exchange.