A PCN LIGAND SYSTEM - EXCLUSIVE C-C ACTIVATION WITH RHODIUM(I) AND C-H ACTIVATION WITH PLATINUM(II)

Reaction of the new aromatic aminophosphine ligand tert-butylphosphino )methyl)-2,4,6-trimethylbenzene (4) with [Rh(COE)(2)Cl](2) (COE = cycl ooctene) or with [Rh(ethylene)(2)Cl](2) at room temperature results in selective carbon-carbon bond activation, yielding the complex Rh(CH3) [C6H(CH3)(2)(CH2N(C2H5)(2))(CH2P(t-Bu)(2))] (5). No competing C-H acti vation was observed during the course of the reaction. When 4 was reac ted with (COD)PtCl2 (GOD = cyclooctadiene), selective C-H activation o f the methyl group situated between the phosphine and amine groups too k place, with concomitant intramolecular H transfer to the amine ligan d, resulting in the zwitterionic Pt(II) complex H2(C6H(CH3)(2)(CH2NH(C 2H5)(2))(CH2P(t-Bu)(2))(11).