title: Methylidene rare-earth-metal complex mediated transformations of C=N, N=N and N-H bonds: new routes to imido rare-earth-metal clusters.
abstract: Three new patterns of reactivity of rare-earth metal methylidene complexes have been established and thus have resulted in access to a wide variety of imido rare-earth metal complexes [L3Ln3(μ2-Me)3(μ3-Me)(μ-NR)] (L = [PhC(NC6H3iPr2-2,6)2](-); R = Ph, Ln = Y (2 a), Lu (2 b); R = 2,6-Me2C6H3, Ln = Y (3 a), Lu (3 b); R = p-ClC6H4, Ln = Y (4 a), Lu (4 b); R = p-MeOC6H4, Ln = Y (5 a), Lu (5 b); R = Me2CHCH2CH2, Ln = Y (6 a), Lu (6 b)) and [{L3Lu3(μ2-Me)3(μ3-Me)}2(μ-NR'N)] (R' = (CH2)6 (7 b), (C6H4)2 (8 b)). Complex 2 b was treated with an excess of CO2 to give the corresponding carboxylate complex [L3Lu3(μ-η(1):η(1)-O2CCH3)3(μ-η(1):η(2)-O2C-CH3)(μ-η(1):η(1):η(2)-O2CNPh)] (9 b) easily. Complex 2 a could undergo the selective μ3-Me abstraction reaction with phenyl acetylene to give the mixed imido/alkynide complex [L3Y3(μ2-Me)3(μ3-η(1):η(1):η(3)-NPh)(μ3-C≡CPh)] (10 a) in high yield. Treatment of 2 with one equivalent of thiophenol gave the selective μ3-methyl-abstracted products [L3Ln3(μ2-Me)3(μ3-η(1):η(1):η(3)-NPh)(μ3-SPh)] (Ln = Y (11 a); Lu (11 b). All new complexes have been characterized by elemental analysis, NMR spectroscopy, and most of the structures confirmed by X-ray diffraction.
authors.affiliation: Department of Chemistry, Fudan University, Shanghai 200433, PR China.
authors.forename: Jianquan
authors.initials: J
authors.lastname: Hong
authors.forename: Lixin
authors.initials: L
authors.lastname: Zhang
authors.forename: Kai
authors.initials: K
authors.lastname: Wang
authors.forename: Yin
authors.initials: Y
authors.lastname: Zhang
authors.forename: Linhong
authors.initials: L
authors.lastname: Weng
authors.forename: Xigeng
authors.initials: X
authors.lastname: Zhou
mesh_terms: D001391:Azo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D007097:Imines / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008674:Metals, Rare Earth / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010636:Phenols; D013438:Sulfhydryl Compounds; D014961:X-Ray Diffraction
chemical_list: D001391:Azo Compounds; D007097:Imines; D008674:Metals, Rare Earth; D009942:Organometallic Compounds; D010636:Phenols; D013438:Sulfhydryl Compounds; C042983:thiophenol