The catalytic dechlorination of aryl chlorides performed by RuHCl(H-2)(2)(P
Cy3)(2) and RuH2(H-2)(2)(PCy3)(2) in alcohols is rapid and complete within
1 h. The mechanism involves a transfer hydrogenation step with participatio
n of the alcohol. The system exhibits significant functional group toleranc
e. The catalyst can be generated in situ from [RuCl2(COD)](x) (COD = cycloo
ctadiene) and 2 equiv of phosphine (PCy3 or (PPr3)-Pr-i). Catalytic convers
ions are similar to those observed when an isolated precatalyst is used. Me
chanistic considerations and the scope of the process are discussed.