桥联脒基稀土芳氧配合物的合成及其催化性能的分析-synthesis and catalytic performance analysis of bridged amidino rare earth aryloxy complexes.docxVIP

 PAGE 4 桥联脒基稀土芳氧配合物的合成及其催化性能的研究 英文摘要 Syntheses and catalytic behavior of bridged bis(amidinate) lanthanide aryloxides ABSTRACT A series of lanthanide aryloxide complexes LLn(OAr)(DME) supported by linked bis(amidinate)s (L = [Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3]) were synthesized and fully characterized. The catalytic activity of these complexes for guanylation of amines with carbodiimides was tested. The main results obtained are as follows: Reactions of LLnCl(THF)2 with NaOAr in THF afforded various bridged bis(amidinate)s lanthanide aryloxides LLnOAr(DME) (L = Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3, DME = dimethoxyethane, Ln = Y, Ar = 2,6-Me2C6H3 (1), 2,6-iPr2C6H3 (2), 4-Me-2,6-tBu2C6H2 (3); Ar = 4-Me-2,6-tBu2C6H2, Ln = Nd (4), Sm (5), Yb (6)). These complexes were characterized by elemental analysis, IR spectroscopy, and complexes 1-3 were characterized by NMR spectroscopy. The state structures of these complexes were studied by X-ray diffraction. The complexes of LLnOAr(DME) are efficient precatalysts for catalytic addition of amines to carbodiimides, and factors affect the catalyst screening system, the amount of catalyst, temperature, solvent etc. To compare the mode reactions with Ln(OAr)3(THF)2 respectively, were also conducted. The catalytic addition reaction with 3 showed a good scope of substrates. In order to gain information about the real active species and the reaction pathways, the reaction of 6 with iPrNCNiPr in a 1 : 1 molar ratio was firstly carried out in toluene at 60 oC. However, after stirring for 24 h, no reaction was observed and complex 6 was recovered completely from the reaction solution. The reaction of 6 with PhNH2 at a molar ratio of 1 : 1 was then carried out at 60 oC. The reaction took place smoothly, and the bis-aryloxide complex supported by a newly formed amidine-functionalized monoamidinate ligand L’, L’Yb[O4-Me-2,6-tBu2C6H2]2 (7) (L’ = Me3SiNHC(Ph)N(CH2)3NC(Ph)NSiMe3) was isolated in 42.6% yield. Then, the reaction of 6 with