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

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posted on 14.02.2005, 00:00 authored by Jie Zhang, Liping Ma, Ruifang Cai, Linhong Weng, Xigeng Zhou
[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-η13-OSNC7H4)]2 (3), while Cp2Yb(p-H2NC6H4S)(THF) (2) reacts with PhNCO under the same conditions to form the simple insertion product {Cp2Yb[μ-η13-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.