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（英文）

发布时间：2018-02-03 02:57

本文关键词： 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　出处：《无机化学学报》2017年11期 　论文类型：期刊论文

【摘要】：Cp_3Ln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-η~2∶η~2-NHC_6H_4CONH)(μ_3-η~1∶η~1∶η~2-NHC_6H_4CONH)LnCp(HMPA)}2(Ln=Yb,1a;Er,1b;Y,1c)。化合物1与4倍物质的量的Ph NCO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Ar CONH-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~1c与i Pr N=C=NiPr反应,仅得到Ar NH基单加成产物{Cp——2Ln[μ-η~1∶η~1∶η~2-iPrNC(NHiPr)NC_6H_4CONH]}3Ln(HMPA)3(Ln=Yb,3a;Er,3b;Y,3c)。而Cp3Ln与邻氨基苯甲酰胺和i Pr N=C=Ni Pr在甲苯中进行"一锅"反应,则形成双核配合物{CpLn[μ-η~1∶η~2∶η~2-NHCOC_6H_4NC(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。
[Abstract]:Cp_3Ln reacts with o-aminobenzoamide in toluene, then crystallizes in HMPA and toluene to obtain tetranuclear rare earth organic complexes in medium to high yield. [CpLn (渭-畏 2: 畏 2: 畏 2-NHCs 6 H4CONH1 (渭-畏 1: 畏 1: 畏 2-NHCT 6H 4CONH / LnCpPU HMPAs)). } 2Ln Yb. 1a; Ernst 1b; Compound 1 reacts with 4 times the amount of Ph NCO in toluene to form 1 / 3-quinazoline dioxy Quo) double anion rare earth complex. [Cp2Ln (渭 3- 畏 2: 畏 2: 畏 1-Quo)] 3LnPa-HMPA-2LnPa-YbPU 2a; Cp2Ln (渭 3- 畏 2: 畏 2: 畏 1-Quo); Ernst 2b; The results show that the Ln-NHAr bond and ar CONH-Ln bond in compound 1 have a continuous addition / amine elimination reaction with isocyanate molecules to form 1. 3-quinazoline dioxy group skeleton. However, compound 1a ~ (1) C reacted with iPr N ~ (2 +) C ~ (2 +) NiPr to obtain only the ar NH group monoaddition product {Cp--2Ln. [渭-畏 1: 畏 1: 畏 2-iPrNCU NHiPrNCU NC6H4CONH]} 3LnPa-HMPA3 LnPa-YbC3a; Ernst 3b; The binuclear complex {CpLn was formed when Cp3Ln reacted with o-aminobenzoamide and I pr NCU Ni pr in a "one pot" reaction in toluene. [渭-畏 1: 畏 2: 畏 n 2 NHCOC\ + 6 H4NCX / NHiPrNiPr]} 2Lnn (Yb) 4a; Ernst 4b; It is important to note that HMPA can induce ligand 4 to form compound 3.
【作者单位】：复旦大学化学系上海市分子催化与功能材料重点实验室;金属有机化学国家重点实验室;
【基金】：国家自然科学基金(No.21372047,21572034)资助项目
【分类号】：O621.25;O641.4
【正文快照】： 0 IntroductionThere is currently a fundamental interest in thereactivity of organolanthanide complexes toward unsa-turated small molecules,because this is the source fordesign of new catalytic reactions and catalysts[1-6].Theselective insertion of an org

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