Heterolytic carbon-iodine bond cleavage by a palladium(I) metalloradical.

The well-defined Pd(I) metalloradical [Pd(P t Bu 3 ) 2 ] + reacts with aryl and alkyl iodides at room temperature, yielding [Pd(P t Bu 3 )(μ-I)] 2 and phosphonium salts. Pd(II) aryl/alkyl derivates, reflecting net radical oxidative addition of the substrate to the metalloradical, are generated during the reaction and two examples have been isolated and crystallographically characterised.