β-diketone imine compounds of rare earth aryloxy synthesis, characterization and catalytic behavior

Title: β-diketone imine compounds of rare earth aryloxy synthesis, characterization and catalytic behavior
　　Author: Chen Hongxia
　　Degree awarded: Suzhou University
　　Keywords: β-diketone imine;; rare earth complexes;; catalyzed polymerization;; guanidine reaction
　　Summary:
　　In this paper, β-diketone imine supporting ligands for the use of solvent polarity, selective synthesis of dual-and single-core rare-earth β-diketone imine-aryloxy complexes, and crystal structure of them identification. On this basis, further study of Strong magnets some complexes of ε-caprolactone (ε-CL), L-lactide (L-LA), guanidine amine reaction with diimine catalytic behavior. Main results are as follows:
　　1. [(DIPPh) _2nacnac] LnCl_2 (THF) _2 (Ln = Yb, Y) ((DIPPh) _2nacnac = N, N-diisopropylphenyl-2 ,4-pentanediimineanion)) and Na (OAr) (OAr = 2,6 -diisopropylphenoxide) in a 1:1 molar ratio in tetrahydrofuran reaction single-core single-aryloxy rare earth chloride [(DIPPh) _2nacnac] Ln (OAr) Cl (THF) (Ln = Yb (1), Y (2)) . After complex 1 infrared spectroscopy, elemental analysis, characterization, and determination of its crystal structure. After complex 2 1HNMR characterization. In complex 1 under mild conditions can be used as single component catalyst, triggering ε-caprolactone and L-lactide controlled polymerization.
　　2 with [(DIPPh) _2nacnac] LnCl_2 (THF) _2 (Ln = Yb, Sm, Nd), and aryloxy sodium molar ratio of 1:2 according to the reaction in THF, were obtained [(DIPPh) _2nacnac] Yb ( OAr) _2 (OAr = 2,6-diisopropylphenoxide) (3), [(DIPPh) _2nacnac] Nd (OAr ") _2 (OAr" = 2,6-di-tert-butyl-phenoxide) (4), [( DIPPh) _2nacnac] Nd (OAr) _2 (OAr = 2,6-diisopropylphenoxide) (5), [(DIPPh) _2nacnac] Sm (OAr) _2 (OAr = 2,6-diisopropylphenoxide) (6). With Nd (OAr ') _2Cl · 2THF (OAr' = 2,6-Dimethylphenoxide) and [(DIPPh) _2nacnac] Na in a 1:1 molar ratio in THF reaction, the complexes [(DIPPh) _2] Nd (OAr ') _2 (THF) (7). These complexes have been infrared spectroscopy, elemental analysis, characterization, and determination of their crystal structure. 3 complexes under mild conditions in one component can be used as a catalyst to lead to high activity of ε-caprolactone and L-lactide polymerization. Activity much higher than the β-diketone imine stable dual-and single-core single-aryloxy rare earth chloride, but the polymer molecular weight distribution is relatively wide. Studied the complexes 3, 4, 5, 6, 7 amine and two imine catalytic reaction of guanidine, the results show that such a class of rare earth - oxygen bond in trivalent rare earth complexes can be highly active catalytic amine and two imine guanidine reaction, and substrate have better ability to adapt.
　　3. [(DIPPh) _2nacnac] Yb (THF) (μ-Cl) _3Yb (Cl) [(DIPPh) _2nacnac] and Na (OAr ') (OAr' = 2,6-Dimethylphenoxide) and Na (OAr) (OAr = 2,6-diisopropylphenoxide) in a 1:1 molar ratio in toluene were obtained binuclear complexes {[(DIPPh) _2nacnac] Yb (OAr ') (μ-Cl) _3Yb [(DIPPh) _2nacnac] (THF )} (8) and {[(DIPPh) _2nacnac] Yb (OAr) (μ-Cl) _3Yb [(DIPPh) _2nacnac] (THF)} (9), to [(DIPPh) _2nacnac] YbCl_2 (THF) and NaOAr '1:1 molar ratio in toluene has been a dual-core [{(DIPPh) _2nacnac} Yb (OAr')] 2 (μ-Cl) _2 complexes (10). http://www.chinamagnets.biz/ These complexes have been infrared spectroscopy, elemental analysis, characterization, and determination of their crystal structure. In these complexes under mild conditions can be used as single component catalyst for triggering of ε-caprolactone and L-lactide controlled polymerization.
　　4 of the [{(DIPPh) _2nacnac} Yb (OAr ')] 2 (μ-Cl) _2 (10) lead to ε-caprolactone and L-lactide polymerization dynamics, with the polymerization time increase in conversion rate also increased, polymerization time and ln ([M] o / [M]) is linear; molecular weight increased linearly with the conversion rate increases, and the molecular weight distribution (Mw / Mn) remained not change.