Reactivity of Organolanthanide Derivatives Containing the o-Aminothiophenolate Ligand toward Carbodiimide
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- 作者：Liping Ma ; Jie Zhang ; Zhengxing Zhang ; Ruifang Cai ; Zhenxia Chen ; Xigeng Zhou
- 刊名：Organometallics
- 出版年：2006
- 出版时间：September 11, 2006
- 年：2006
- 卷：25
- 期：19
- 页码：4571 - 4578
- 全文大小：237K
- 年卷期：v.25,no.19(September 11, 2006)
- ISSN：1520-6041
文摘
A series of lanthanocene derivatives containing the o-aminothiophenolate ligand have been synthesized,and their reactivities toward carbodiimide have been investigated. Reaction of N,N'-diisopropylcarbodiimide(iPrN=C=NiPr) with [Cp2Yb(o-H2NC6H4S)]2·2THF (Cp = C5H5) (1) yields a centrosymmetric dimer,[Cp(THF)Yb(
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3:1-SC6H4N=C(NHiPr)NiPr)]2 (2), indicating that the adjacent NH2 group can add tothe C=N double bonds of carbodiimide and one cyclopentadienyl group is eliminated. [Cp2Dy(o-H2NC6H4S)]2·3THF, obtained by protolysis of Cp3Ln with o-aminothiophenol, reacts with 2 or 1 equiv ofiPrN=C=NiPr in THF at room temperature to give the partial amino group addition product CpDy(THF)[-3:1-SC6H4N=C(NHiPr)NiPr)](-2:1-SC6H4NH2)DyCp2·THF (4). When Cp3Dy reacts witho-aminothiophenol, and subsequently with iPrN=C=NiPr in toluene at room temperature, we isolatedcomplex 4 and a small amount of [Cp2Dy(o-H2NC6H4S)]2·2THF (5) and [Cp(THF)Dy(-3:1-SC6H4N=C(NHiPr)NiPr)]2 (6). Treatment of 2 equiv of iPrN=C=NiPr with 3 in THF under refluxtemperature also gave 4; the residual NH2 group cannot continuously add into the C=N bonds of othercarbodiimide molecules. Reaction of Cp3Er with 2 equiv of o-aminothiophenol and subsequently with 2equiv of iPrN=C=NiPr in THF at room temperature yields the bis-addition product (C5H5)Er[SC6H4NC(NHiPr)2]2 (7). However, when Cp3Er reacts with 2 equiv of o-aminothiophenol, and subsequentlywith 1 equiv of iPrN=C=NiPr, the organic disulfide (iPrHN)2CNC6H4SSC6H4NC(NHiPr)2 (8) can beisolated. These results indicate that the addition of the adjacent amino group into the C=N double bondsof the carbodiimide molecule is strongly affected by the metal ion character and the steric hindrance ofthe ligands. All of the new compounds have been characterized by elemental analysis and spectroscopicproperties. Their structures have also been determined through X-ray single-crystal diffraction analysis.
-3:1-SC6H4N=C(NHiPr)NiPr)]2 (2), indicating that the adjacent NH2 group can add tothe C=N double bonds of carbodiimide and one cyclopentadienyl group is eliminated. [Cp2Dy(o-H2NC6H4S)]2·3THF, obtained by protolysis of Cp3Ln with o-aminothiophenol, reacts with 2 or 1 equiv ofiPrN=C=NiPr in THF at room temperature to give the partial amino group addition product CpDy(THF)[-3:1-SC6H4N=C(NHiPr)NiPr)](-2:1-SC6H4NH2)DyCp2·THF (4). When Cp3Dy reacts witho-aminothiophenol, and subsequently with iPrN=C=NiPr in toluene at room temperature, we isolatedcomplex 4 and a small amount of [Cp2Dy(o-H2NC6H4S)]2·2THF (5) and [Cp(THF)Dy(-3:1-SC6H4N=C(NHiPr)NiPr)]2 (6). Treatment of 2 equiv of iPrN=C=NiPr with 3 in THF under refluxtemperature also gave 4; the residual NH2 group cannot continuously add into the C=N bonds of othercarbodiimide molecules. Reaction of Cp3Er with 2 equiv of o-aminothiophenol and subsequently with 2equiv of iPrN=C=NiPr in THF at room temperature yields the bis-addition product (C5H5)Er[SC6H4NC(NHiPr)2]2 (7). However, when Cp3Er reacts with 2 equiv of o-aminothiophenol, and subsequentlywith 1 equiv of iPrN=C=NiPr, the organic disulfide (iPrHN)2CNC6H4SSC6H4NC(NHiPr)2 (8) can beisolated. These results indicate that the addition of the adjacent amino group into the C=N double bondsof the carbodiimide molecule is strongly affected by the metal ion character and the steric hindrance ofthe ligands. All of the new compounds have been characterized by elemental analysis and spectroscopicproperties. Their structures have also been determined through X-ray single-crystal diffraction analysis.© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |