N,N-Dialkyl-2-iodoanilines: a versatile source for the synthesis of Pd(ii) complexes. Synthesis of novel OCP- and CCN-pincer palladium complexes.

The reactivity of a series of N,N-dimethyl-2-iodoanilines bearing different chelating "arms" at the 3-position with Pd(2)(dba)(3) has been explored. 3-[(Diphenylphosphino)methyl]-2-iodo-N,N-dimethylaniline reacted with Pd(2)(dba)(3) and PPh(3) under aerobic conditions to give the OCP-pincer complex , which was formed by sequential C(sp(3))-H activation/oxidation at the alpha-position of the aniline N atom. On the other hand, under similar reaction conditions, 3-[2-(dimethylamino)ethyl]-2-iodo-N,N-dimethylaniline afforded the CCN-pincer complex , after a second C-H activation process at the formyl group of the initially formed OCN-pincer complex. In contrast, 2-iodo-3-(1H-1,2,4-triazol-1-ylmethyl)-N,N-dimethylaniline and 2-iodo-3-(pyrazol-1-ylmethyl)-N,N-dimethylaniline reacted with Pd(2)(dba)(3) and PPh(3), respectively, to give the 6-membered azapalladacycles and , in which the aniline nitrogen is merely a spectator substituent. Finally, treatment of iodide complex with Tl(TfO) afforded the CN-bidentate cationic complex. Solid-state structures of palladium complexes, and CH(2)Cl(2).3CH(3)OH.5H(2)O were determined by X-ray analysis.