CYCLOPALLADATION OF SECONDARY AND PRIMARY BENZYLAMINES

Benzylamine as well as secondary benzylamines react with palladium(II) acetate in benzene to give the dinuclear cyclopalladated complexes [(Pd(mu-O(2)CMe)(C(6)H(4)CH(2)NHR))(2)] (R=H, Me, Pr-i, Ph). These complexes are converted into the chloro-bridged complexes [(Pd(mu-Cl)(C(6)H(4)CH(2)NHR))(2)] by metathetical reactions with sodium chloride. The chloro-bridged dimers undergo bridge-splitting reactions with 3,5-lutidine, triphenylphosphine, thallium(I) acetylacetonate, etc. affording the corresponding mononuclear cyclopalladated complexes [PdCl(C(6)H(4)CH(2)NHR)L] (L=3,5-lutidine, PPh(3), etc.) and [Pd(C(6)H(4)CH(2)NHR)(acac)]. The H-1 NMR spectra confirm their cyclopalladated features. N-Neopentylbenzylamine, which has two possibilities to be palladated at the sp(2) carbon of the benzyl moiety or the sp(3) carbon of the neopentyl moiety, gives the 2(N-neopentylarninomethyl)phenyl-C-1,N chelate ring.