Formation of P,C-chelated palladium complexes by phosphine-assisted oxidative addition of an aliphatic CCl bond

Reactions of the (chloralkyl) phosphine 1-chloro-3-(diisopropylphosphino)propane ( 3) with chelated Pd(0) complexes have been given, leading to P,C-chelated complexes. Reaction of a methyl-π-allypalladium chloride dimer with 1,3-(diisopropylphosphino)propane and a base gives the binuclear complex 2a. Pd(dippe) 2 (dippe = 1,2-bis(diisopropylphosphino)ethane) reacts with 3 to yield the mononuclear bis-chelated complex 6. As expected, the intramolecular coordinatively oxidative addition of the aliphatic CCl bond in 3 to the metal center is much faster than that of the intermolecular reaction of n-butyl chloride. The X-ray structure of 2a was determined.