Substituent Effects on Isocyanate Insertion into a Lanthanide−Sulfur Bond. Unexpected Construction of a Coordinated Thiazolate Ring

• Published in: Organometallics Vol. 24; no. 4; pp. 738 - 742
• Main Authors: Zhang, Jie, Ma, Liping, Cai, Ruifang, Weng, Linhong, Zhou, Xigeng
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 14.02.2005; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Physical Sciences; Science & Technology; SIGMA-BOND; ORGANOLANTHANIDE COMPLEXES; LIGANDS; SCOPE; X-RAY; REACTIVITY; CRYSTAL-STRUCTURES; INTRAMOLECULAR HYDROPHOSPHINATION/CYCLIZATION; PHENYL ISOCYANATE; F-ELEMENT COMPLEXES
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om0492606

[Cp2Yb(o-H2NC6H4S)]2·2THF (1) and Cp2Yb(p-H2NC6H4S)(THF) (2) were prepared in good yields by the protonolysis of Cp3Yb with the corresponding amino-substituted thiophenol in THF at room temperature, respectively. Treatment of [Cp2Yb(o-H2NC6H4S)]2·2THF (1) with PhNCO gives the unexpected intermolecular addition/cyclization/elimination product [(C5H5)2Yb(μ-η1:η3-OSNC7H4)]2 (3), while Cp2Yb(p-H2NC6H4S)(THF) (2) reacts with PhNCO under the same conditions to form the simple insertion product {Cp2Yb[μ-η1:η3-OC(p-H2NC6H4S)NPh]}2·2THF (4), demonstrating that the neighboring NH2 group participation could lead to unique isocyanate insertion reactivity. The structures of all the complexes were confirmed by X-ray single-crystal diffraction analysis, indicating that complexes 1 and 4 have an unusual intermolecular hydrogen bond interaction involving THF, and a novel intramolecular π−π weak interaction between aromatic rings is also observed in 4.