title: Synthesis, characterization of bridged bis(amidinate) lanthanide amides and their application as catalysts for addition of amines to nitriles for monosubstituted N-arylamidines.
abstract: A series of lanthanide amide complexes supported by bridged bis(amidinate) ligand L, LLnNHAr(1)(DME) (L = [Me(3)SiNC(Ph)N(CH(2))(3)NC(Ph)NSiMe(3)], Ar(1) = 2,6-(i)Pr(2)C(6)H(3), DME = dimethoxyethane, Ln = Y (1), Pr (2), Nd (3), Gd (4), Yb (5)), [Yb(μ(2)-NHPh)](2)(μ(2)-L)(2) (6) and [LYb](2)(μ(2)-NHAr(2))(2) (7) (Ar(2) = (o-OMe)C(6)H(4)), were synthesized by reaction of LLnCl(THF)(2) with the corresponding lithium amide in good yields and structurally characterized by X-ray crystal structure analyses. All complexes were found to be precatalysts for the catalytic addition of aromatic amines to aromatic nitriles to give monosubstituted N-arylamidines. The catalytic activity was influenced by lanthanide metals and the amido groups with the active sequence of Y (1) < Gd (4) < Nd (3) < Pr (2) ∼ Yb (5) for the lanthanide metals and -NHAr(2) < -NHPh < -NHAr(1) for the amido groups. The catalytic addition reaction with complex 5 showed a good scope of aromatic amines. Some key reaction intermediates were isolated and structurally characterized, including the amidinate complexes LLn[NPhCNAr(1)](PhCN) (Ln = Y (8), Ln = Yb (9)), LYb[NAr(2)CNAr(1)](Ar(2)CN) (10), and amide complex 5 prepared by protonation of 9 by Ar(1)NH(2). Reactivity studies of these complexes suggest that the present catalytic formation of monosubstituted N-arylamidines proceeds through nucleophilic addition of an amido species to a nitrile, followed by amine protonolysis of the resultant amidinate species.
authors.affiliation: Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China.
authors.forename: Wenbo
authors.initials: W
authors.lastname: Li
authors.forename: Mingqiang
authors.initials: M
authors.lastname: Xue
authors.forename: Fan
authors.initials: F
authors.lastname: Xu
authors.forename: Jing
authors.initials: J
authors.lastname: Tu
authors.forename: Yong
authors.initials: Y
authors.lastname: Zhang
authors.forename: Qi
authors.initials: Q
authors.lastname: Shen
mesh_terms: D000577:Amides / Q000737:chemistry*; D000578:Amidines / Q000138:chemical synthesis / Q000737:chemistry*; D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008968:Molecular Conformation; D009570:Nitriles / Q000737:chemistry*
chemical_list: D000577:Amides; D000578:Amidines; D000588:Amines; D056831:Coordination Complexes; D028581:Lanthanoid Series Elements; D009570:Nitriles