The platinum-catalyzed hydroamination of ethylene with aniline is reported for the first time. Using PtBr2 as a catalyst precursor in n-Bu4PBr under 25 bar of ethylene pressure affords N-ethylaniline with 80 turnovers after 10 h at 150 °C. The reaction simultaneously produces 2-methylquinoline in ca. 10 cycles. The catalytic activity is slightly improved by increasing the reaction temperature or the ethylene pressure and strongly depends on the aniline/platinum ratio. The beneficial effects of added P(OMe)3 (2 equiv/PtBr2) or of a proton source (3 equiv/PtBr2) have also been pointed out. A gradual poisoning by N-ethylaniline has been observed, which could be minimized by using biphasic systems. The best result for the hydroamination with aniline (TON = 145 after 10 h at 150 °C) has been obtained in a biphasic system (n-Bu4PBr/decane) in the presence of C6H5NH3 + (3 equiv/PtBr2). The basicity of the arylamine has been shown to play an important role:  the lower the basicity, the higher the TON. Thus, the hydroamination of ethylene with the weakly basic 2-chloroaniline in the presence of the PtBr2/H+ catalytic system (0.3% mol) for 72 h at 150 °C yields N-ethyl-2-chloroaniline as the sole reaction product (70% yield based on the amine charged) with TON = 250. When conducted with 1% of the above catalytic system, the reaction resulted in nearly quantitative conversion of 2-chloroaniline.

The cyclopalladation of a series of symmetric diimines with the formula (RC 6 H 4 CHNZ) 2 , where Z = CH 2 or (CH 2 ) 2 OCH 2 and R = p-Cl, p-OMe, p-NO 2 , and o-Cl, is described. Optimal conditions to obtain the dimetalated compounds were found to be palladium(II) acetate, in toluene, at 60 °C and with a reaction time of 2−4 h. The reactivity of the dimetalated compounds with monodentate, bidentate, and bis(monodentate) Lewis bases was also studied. The cytotoxic activity of some selected compounds was evaluated against a panel of adenocarcinoma cell lines (colon HCT116 and breast MCF7 and MDA-MB231). Compounds containing the fragment NCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 N exhibited a remarkable cytotoxic activity in the three cancer cells assayed, but complexes containing the NCH 2 CH 2 N fragment showed no activity. It seems that the length and flexibility of the central saturated chain in the imine molecule, as well as its lipophilicity and hydrophilicity, explain the different cytotoxicity of the two series of coordination compounds here reported.