C–O and C–N Functionalization of Cationic, NCN-Type Pincer Complexes of Trivalent Nickel: Mechanism, Selectivity, and Kinetic Isotope Effect

This report presents the synthesis of new mono- and dicationic NCN-NiIII complexes and describes their reactivities with protic substrates. (NCN is the pincer-type ligand κ N , κ C , κ N-2,6-(CH2NMe2)2-C6H3.) Treating van Koten’s trivalent complex (NCN)­NiIIIBr2 with AgSbF6 in acetonitrile gives the dicationic complex [(NCN)­NiIII(MeCN)3]2+, whereas the latter complex undergoes a ligand-exchange reaction with (NCN)­NiIIIBr2 to furnish the related monocationic complex [(NCN)­NiIII(Br)­(MeCN)]+. These trivalent complexes have been characterized by X-ray diffraction analysis and EPR spectroscopy. Treating these trivalent complexes with methanol and methylamine led, respectively, to C-OCH3 or C-NH­(CH3) functionalization of the Ni-aryl moiety in these complexes, C-heteroatom bond formation taking place at the ipso-C. These reactions also generate the cationic divalent complex [(NCN)­NiII(NCMe)]+, which was prepared independently and characterized fully. The unanticipated formation of the latter divalent species suggested a comproportionation side reaction between the cationic trivalent precursors and a monovalent species generated at the C–O and C–N bond formation steps; this scenario was supported by direct reaction of the trivalent complexes with the monovalent compound (PPh3)3NiICl. Kinetic measurements and density functional theory analysis have been used to investigate the mechanism of these C–O and C–N functionalization reactions and to rationalize the observed inverse kinetic isotope effect in the reaction of [(NCN)­NiIII(Br)­(MeCN)]+ with CH3OH/CD3OD.