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Synthesis and Characterization of Race-earth Metal Complexes Stabilized by Phenoxy-amido Ligands and Their Catalytic Behavior

Author: HuangLingLing
Tutor: YaoYingMing
School: Suzhou University
Course: Organic Chemistry
Keywords: aminophenol lanthanide amidation guanylation catalyze
CLC: O643.3
Type: Master's thesis
Year: 2011
Downloads: 31
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Abstract


A series of phenoxy-amido rare-earth metal complexes supported by the dianionic phenoxy-amido ligands were synthesized. The catalytic activities of anionic phenoxy-amido for the amidation of aldehydes with amines and of neutral phenoxy-amido rare-earth metal amide for the guanylation of amines with carbodiimide were examined.The aminophenol ligands used in this thesis are as follows:N-p-fluoro-phenyl（2-hydroxy-3,5-di-tert-butyl）benzylamine [NO]1H2,N-p-methyl-phenyl（2-hydroxy-3,5-di-tert-butyl）benzylamine [NO]2H2,N-p-chloro-phenyl（2-hydroxy-3,5-di-tert-butyl）benzylamine [NO]3H2,N-p-bromo-phenyl（2-hydroxy-3,5-di-tert-butyl）benzylamine [NO]4H2,N-p-methoxyl-phenyl（2-hydroxy-3,5-di-tert-butyl）benzylamine [NO]5H2The main results obtained are as follows:1. The anionic rare-earth metal amido complexes stabilized by phenoxy-amido ligand [NO]21Ln[N（TMS）2][Li（THF）]2 [Ln = Y（1）, Yb（2）, Sm（3）, Nd（4）], [NO]22Sm[N（TMS）2][Li（THF）]2 （5）, [NO]23Sm[N（TMS）2][Li（THF）]2 （6）, [NO]24Sm[N（TMS）2][Li（THF）]2 （7） were prepared according to the literature in high isolated yields. It was found that complexes 1-7 are active catalysts for amidation of aldehydes with amines. The new catalysts show high activity and a wide range of scope to produce amides in good to excellent yields under mild conditions. A cooperation effect between lanthanide and alkali metals for high activity is proposed.2. The catalytic activity of some lanthanide-potassium heterobimetallic complexes stabilized by carbon-bridged bis（phenolate） ligand for amidation of aldehydes with amines were also tested. It was found that the ionic radii of the lanthanide metals have a significant effect on the catalytic activity. Although the conditions are a litter rigorous, the catalysts show a wide rang of scope to produce amides.3. Reaction of of Ln[N（TMS）2]3（μ-Cl）Li（THF）3 with the lithium aminophenoxy in 1:2 molar ratio generated in situ in tetrahydrofuran （THF） gave the anionic rare-earth metal complexes [NO]35Ln[Li（THF）]3 [Ln = Y（13）, Yb（14）, Sm（15）, Nd（16）]. Complexes 13-16 were fully characterized by IR and elemental analysis and single crystal X-Ray diffraction. Structural determination revealed that they are isostructural.4. Reaction of of Ln[N（TMS）2]3（μ-Cl）Li（THF）3 with aminophenol [NO]5H2 in 1:1 molar ratio in THF gave the neutral phenoxy-amido rare-earth metal amide {[NO]5Ln[N（TMS）2]（THF）}2 [Ln = Sm（17）, Nd（18）, La（19）], whereas an ion-pair rare-earth metal complexe [{NO}35Yb2（μ-Cl）（THF）2][Li（THF）4] （20） was isolated under the same reaction conditions when Yb[N（TMS）2]3（μ-Cl）Li（THF）3 was used as starting materials. Complexes 17-20 were fully characterized by IR and elemental analysis and single crystal X-Ray diffraction.5. Complexes 17-19 serve as excellent catalyst precursors for catalytic addition of various primary amines to carbodiimides, efficiently providing the corresponding guanidine derivatives with a wide range of substrates under solvent-free condition. The reaction shows good functional groups tolerance.

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CLC: > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Chemical kinetics,catalysis > Catalytic
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