Palladium(II) complexes of unsymmetrical CNN pincer ligands

Unsymmetrical 1-(arylimino)-3-(2-hetarylimino)isoindolines have been prepared from 1,3-diiminoisoindoline, an arylamine (aniline, 2-methylaniline, 2-iodoaniline), and a heteroaromatic amine (2-amino-6-methylpyridine, 2-amino-4-methylthiazole) in a stepwise manner by two consecutive condensations. The metalation reactions of these compounds with palladium(II) acetate proceed upon cyclopalladation of the carbocyclic aryl moieties and yield unsymmetrical C,N,N pincer complexes in all cases. X-ray crystallographic analysis were performed on single crystals of hydrogen[acetato[1-phenylimino-3-(6-methylpyridylimino)isoindolinato]palladate(II)} H[(phpi)Pd(OAc)] and pyridine[1-(2-tolylimino)-3-(4-methylthiazolylimino)isoindolinato]palladium(II) [(2-tolti)Pd(py)] by which the coordination mode, the conformation, the protonation site, and the trans influence of the carbon donor were established. For one more C,N,N pincer complex, hydrogenjacetato[1-(2-iodophenylimino)-3-(6-methylpyridylimino)isoindolinato]palladate(II)} H[(2-lphpi)Pd(OAc)], a similar, mononuclear coordination mode was confirmed by H-1 NMR spectroscopy, whereas for the product of an oxidative addition reaction of a palladium(0) precursor to the iodoaryl derivative a product with exo coordination was found. First experiments showed the effectivity of one of these complexes as a precatalyst in CC coupling reactions (Heck and Stille coupling).