C-H and C-N Bond Activation of Tertiary Amines by Cationic Germanium(IV) Corrole

C-H and C-N bonds in tertiary amines were activated by the germanium(IV) corrole cation [(TPFC)Ge](+) (TPFC = 5,10,15-tris(pentafluorophenyl) corrole) at room temperature. Cleavage of C-H bonds with a unique selectivity for the beta- and gamma-positions in tertiary amines was observed, in contrary to the well-studied alpha-position selectivity in C-H bond cleavage promoted by transition-metal compounds. Preliminary mechanism studies using density functional theory (DFT) calculation indicated a nucleophilic substitution pathway for C-N bond activation. Although the mechanism for the C-H bond activation was not clear at the present stage, a cooperative Lewis acid/base reaction pathway was also calculated.