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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。
Cp_3Ln is reacted with anthranilamide in toluene and then crystallized in HMPA and toluene to obtain a quadruple rare earth organic complex [CpLn (μ-η ~ 2ηη ~ 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). The Ph NCO in the amount of Compound 1 and the amount of 4-fold react in toluene to form a Quo dianion complex [Cp2Ln (μ3-η2: η2: η1-Quo)] 3Ln HMPA) 2 (Ln = Yb, 2a; Er, 2b; Y, 2c) showed that Ln-NHAr bond and Ar CONH-Ln bond in compound 1 could undergo continuous addition / amine elimination reaction with isocyanate molecules to form 1, 3-Quinazoline dioxy skeleton. However, compounds 1a-1c reacted with iPrN = C = NiPr to obtain only the ArNH-based monoadduct {Cp- 2Ln [μ- η ~ 1: η ~ 1: η ~ 2-iPrNC (NHiPr) NC_6H_4CONH] } 3Ln (HMPA) 3 (Ln = Yb, 3a; Er, 3b; Y, 3c). While Cp3Ln is reacted with anthranilamide and i Pr N = C = Ni Pr in a “one-pot” reaction in toluene to form the dinuclear complex {CpLn [μ-η ~ 1: -NHCOC_6H_4NC (NHiPr) NiPr]} 2 (Ln = Yb, 4a; Er, 4b; Y, 4c). It is noteworthy that HMPA can induce ligand 4 to undergo ligand rearrangement reaction and transform into compound 3.