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

Citations Over TimeTop 10% of 2008 papers

Abstract

Various divalent lanthanide complexes with the formula LnL2(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-((t)Bu)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 tolerance. 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.

Related Papers

• → Luminescence Study of the Samarium(II) Sites in Samarium: Barium Octaborate as Differentiated by Excitation Wavelength and Temperature(2017)10 cited
• → Initial stages of the interaction with oxygen of samarium thin films grown on the iridium surface(2014)5 cited
• → Comparison of shape memory behavior and properties of iron-based shape memory alloys containing samarium addition(2006)8 cited
• → Directed Metalation of Arenes with Organolithiums, Lithium Amides, and Superbases(2015)9 cited
• SYNTHESIS AND SPECTRAL CHARACTERISTICS OF DIVALENT SAMARIUM ACTIVATED BINARY FLUORIDES(1993)