Divalent Lanthanide Complexes: Highly Active Precatalysts for the Addition of N-H and C-H Bonds to Carbodiimides

Various divalent lanthanide complexes with the formula LnL(2)(sol)(x) (L = N(TMS)(2), sol = THF, x = 3, Ln = Sm (I), Eu (II), Yb (III); L = MeC5H4, sol = THF, x = 2, Ln = Sm (IV); L = ArO(Ar = [2,6-((BU)-B-t)(2)-4-MeC6H2]), sol = THF, x = 2, Ln = Sm (V)), especially complexes I-III, serve as excellent catalyst precursors for catalytic addition of various primary and secondary amines to carbodiimides, efficiently providing the corresponding guanidine derivatives with a wide range of substrates under solvent-free condition. The reaction shows good functional groups tolerence. Complexes I-III are also excellent precatalysts for addition of terminal alkynes to carbodiimides yielding a series of propiolamidines. The active sequence of Yb < Eu < Sm for metal and MeC5H4 < ArO < N(TMS)(2) for ligand around the metal was observed for both reactions. The first step in both reactions was supposed to include the formation of a bimetallic bisamidinate samarium species originating from the reduction-coupling reaction of carbodiimide promoted by lanthanide(II) complex. The active species is proposed to be a lanthanide guanidinate and a lanthanide amidinate.