Substituent Effects on Isocyanate Insertion into a Lanthanide-Sulfur Bond. Unexpected Construction of a Coordinated Thiazolate Ring
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- 作者：Jie Zhang ; Liping Ma ; Ruifang Cai ; Linhong Weng ; and Xigeng Zhou
- 刊名：Organometallics
- 出版年：2005
- 出版时间：February 14, 2005
- 年：2005
- 卷：24
- 期：4
- 页码：738 - 742
- 全文大小：150K
- 年卷期：v.24,no.4(February 14, 2005)
- ISSN：1520-6041
文摘
[Cp2Yb(o-H2NC6H4S)]2·2THF (1) and Cp2Yb(p-H2NC6H4S)(THF) (2) were prepared in goodyields by the protonolysis of Cp3Yb with the corresponding amino-substituted thiophenol inTHF at room temperature, respectively. Treatment of [Cp2Yb(o-H2NC6H4S)]2·2THF (1) withPhNCO gives the unexpected intermolecular addition/cyclization/elimination product [(C5H5)2Yb(
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1:3-OSNC7H4)]2 (3), while Cp2Yb(p-H2NC6H4S)(THF) (2) reacts with PhNCO underthe same conditions to form the simple insertion product {Cp2Yb[-1:3-OC(p-H2NC6H4S)NPh]}2·2THF (4), demonstrating that the neighboring NH2 group participation could leadto unique isocyanate insertion reactivity. The structures of all the complexes were confirmedby X-ray single-crystal diffraction analysis, indicating that complexes 1 and 4 have anunusual intermolecular hydrogen bond interaction involving THF, and a novel intramolecular
- weak interaction between aromatic rings is also observed in 4.
-1:3-OSNC7H4)]2 (3), while Cp2Yb(p-H2NC6H4S)(THF) (2) reacts with PhNCO underthe same conditions to form the simple insertion product {Cp2Yb[-1:3-OC(p-H2NC6H4S)NPh]}2·2THF (4), demonstrating that the neighboring NH2 group participation could leadto unique isocyanate insertion reactivity. The structures of all the complexes were confirmedby X-ray single-crystal diffraction analysis, indicating that complexes 1 and 4 have anunusual intermolecular hydrogen bond interaction involving THF, and a novel intramolecular- weak interaction between aromatic rings is also observed in 4.