| 茂基稀土邻氨基苯甲酰胺基双负离子配合物的合成及其环胺羰化反应和脒基化反应研究 |
| Synthesis and Cycloaminocarbonylation as well as Amidination of Rare Earth o-Aminobenzamido Dianion Complexes Bearing Cyclopentadienyl Co-ligand |
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| 摘要: Cp3Ln与邻氨基苯甲酰胺在甲苯中反应，伴随着在HMPA和甲苯中结晶，以中等到优秀收率得到四核稀土有机配合物 [CpLn(μ-η2:η2-NHC6H4CONH)(μ3-η1:η1:η2-NHC6H4CONH)LnCp(HMPA)}2 (Ln = Yb(1a), Er(1b), Y(1c))。化合物 1与4当量的PhNCO 在甲苯中反应形成1,3-喹唑啉二氧基(Quo) 双负离子稀土配合物[Cp2Ln(μ3-η2:η2:η1-Quo)]3Ln(HMPA)2 (Ln = Yb(2a), Er(2b), Y(2c))，表明化合物1中的Ln-NHAr键和ArCONH-Ln键能与异氰酸酯分子发生连续加成/胺消除反应，形成1,3-喹唑啉二氧基骨架。但化合物1a-c与iPrN=C=NiPr反应，仅得到ArNH基单加成产物{Cp2Ln[μ-η3:η1-iPrNC(NHiPr)NC6H4CONH]}3Ln(HMPA)3 (Ln = Yb(3a), Er(3b), Y(3c))。而Cp3Ln与邻氨基苯甲酰胺和iPrN=C=NiPr在甲苯中进行“一锅”反应，则形成双核配合物{CpLn[μ-η3:η2-NHCOC6H4NC(NHiPr)NiPr]}2 (Ln = Yb(4a), Er(4b), Y(4c))。值得注意的是，HMPA 能够诱导配合物4发生配体重排反应，转化成化合物3。 |
| 关键词: 环胺羰化反应 异氰酸酯 稀土配合物 邻氨基苯甲酰胺 加成反应 |
| 基金项目: 国家自然科学基金 |
| Abstract: Treatment of Cp3Ln with o-aminobenzamide followed by crystallization in a HMPA and toluene mixture affords the tetranuclear organolanthanide complexes [CpLn(μ-η2:η2-NHC6H4CONH)(μ3-η1:η1:η2-NHC6H4CONH)LnCp(HMPA)}2 (Ln = Yb(1a), Er(1b), Y(1c)). Reaction of 1 with 4 equiv of PhNCO in toluene gives the dianionic quinazolyldiolate (Quo) complexes [Cp2Ln(μ3-η2:η2:η1-Quo)]3Ln(HMPA)2 (Ln = Yb(2a), Er(2b), Y(2c)), indicating that one isocyanate molecule can undergo the tandem reaction with both NH and CONH of 1 to construct a quinazolyldiolate skeleton, companying with the elimination of PhNH2. However, 1a-c react with iPrN=C=NiPr under the same conditions to give only the single ArNH addition products {Cp2Ln[μ-η3:η1-iPrNC(NHiPr)NC6H4CONH]}3Ln(HMPA)3 (Ln = Yb(3a), Er(3b), Y(3c)). Furthermore, treatment of Cp3Ln with o-aminobenzamide followed by reacting with iPrN=C=NiPr gave {CpLn[μ-η3:η2-NHCOC6H4NC(NHiPr)NiPr]}2 (Ln = Yb(4a), Er(4b), Y(4c)). Noticeably, HMPA could induce the transformation of 4 into 3 by a ligand redistribution. |
| Keywords: cycloaminocarbonylation isocyanate lanthanide complexes o-aminobenzamide addition |
| 投稿时间：2017-09-01 修订日期：2017-09-22 |
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