Unusual modification methods for the ureido ligand of lanthanocene derivatives.
(C5H5)2Ln[OC(PzMe2)=NPh](THF) (Ln = Dy (1a), Er (1b), Yb (1c), Y (1d)) were prepared in good yields by the PhNCO insertion into the Ln-N bond of (C(5)H(5))(2)Ln(PzMe(2))(THF) (PzMe(2) = 3,5-dimethylpyrazolate) in THF at room temperature. Treatment of with p-aminothiophenol in THF at room temperature gives unusual ligand-based substitution derivatives {(C5H5)2Ln[mu-eta1:eta3-OC(p-H2NC6H4S)NPh]}2.2THF (Ln = Dy (2a), Er (2b), Yb (2c), Y (2d)), while reaction of 1c with o-aminothiophenol instead of p-aminothiophenol allows the occurrence of a tandem substitution/cyclization/elimination to form unexpected benzothiazole-2-oxide complex [(C5H5)2Yb(mu-eta1:eta3-OSNC7H4)]2 (3c), representing a novel modification method for non-cyclopentadienyl ligands of lanthanocene derivatives. However, complex does not react with benzyl thiol, indicating that the nature of thiols has a profound influence on the substitution reaction. All complexes were characterized by elemental analysis and spectroscopic properties. The X-ray diffraction analysis reveals that and are solvated monomeric structures, while and are centrosymmetric dimeric ones with an unusual intermolecular hydrogen bond interaction involving THF.
Zhang
Jie
J
Department of Chemistry, Molecular Catalysis and Innovative Material Laboratory, Fudan University, Shanghai, 200433, People's Republic of China.
Cai
Ruifang
R
Weng
Linhong
L
Zhou
Xigeng
X