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
Syntheses, Cycloaminocarbonylation and Amidination of Rare Earth o-Aminobenzamido Dianion Complexes Bearing Cyclopentadienyl Co-ligand
作者单位E-mail
孙燕 复旦大学化学系, 上海市分子催化与功能材料重点实验室, 上海 200433  
刘瑞婷 复旦大学化学系, 上海市分子催化与功能材料重点实验室, 上海 200433  
翁林红 复旦大学化学系, 上海市分子催化与功能材料重点实验室, 上海 200433  
周锡庚 复旦大学化学系, 上海市分子催化与功能材料重点实验室, 上海 200433;金属有机化学国家重点实验室, 上海 200032 xgzhou@fudan.edu.cn 
摘要: Cp3Ln与邻氨基苯甲酰胺在甲苯中反应,之后在HMPA和甲苯中结晶,以中等到高收率得到四核稀土有机配合物[CpLn( μ-η2η2-NHC6H4CONH)( μ3-η1η1η2-NHC6H4CONH)LnCp(HMPA)}2(Ln=Yb,1a;Er,1b;Y,1c)。化合物 1与4倍物质的量的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-η2η2η1-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~1ciPrN=C=NiPr反应,仅得到ArNH基单加成产物{Cp2Ln[ μ-η1η1η2-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-η1η2η2-NHCOC6H4 NC(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: 稀土配合物  环胺羰化反应  异氰酸酯  邻氨基苯甲酰胺  加成反应
基金项目: 国家自然科学基金(No.21372047,21572034)资助项目。
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 PhNCO (nPhNCO/n1=4) 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 quinazoly-ldiolate skeleton, companying with the elimination of PhNH2. However, 1a~1c react with iPrN=C=NiPr under the same conditions to give only the single ArNH addition products {Cp2Ln[ μ-η1:η1:η2-iPrNC(NHiPr)NC6H4 CONH]}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-η1:η2: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: lanthanide complexes  cycloaminocarbonylation  isocyanate  o-aminobenzamide  addition
投稿时间:2017-09-01 修订日期:2017-09-22
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孙燕,刘瑞婷,翁林红,周锡庚.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[J].无机化学学报,2017,33(11):2124-2138.
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