柳亞胺基酸之釩氧錯合物的結構、光譜及催化性質研究

The study of structures, spectroscopy, and catalytic properties of salicylideneaminoacidatooxovandium complexes.

黃玄智(Huang Hsuan Chih)

指導教授 ： 蘇展政

國立臺灣師範大學/理學院/化學系/碩士(2000年)

摘要

無資料

關鍵字

釩氧金屬錯合物 ； 催化反應 ； 柳亞胺基酸

並列摘要

The study of vanadium complexes is an important topic in inorganic chemistry and industrial applications. Chiral oxovanadium complexes of the types, [VO(X-sal-D-aminoacid)(L)] and VO(X-sal-L-aminoacid)(L)], have been sythesized, where X-sal-aminoacid stands for Schiff base type condensation products of salicylaldehyde and its 3-methoxy, 5-nitro, and 3,5-di-tert-butyl derivatives, with aminoacids, which include D-valine, L-valine, L-leucine, L-tert-leucine, L-theronine and L-theronine methyl ester, and L represents H2O, CH3OH and C2H5OH. These complexes have been characterized by elemental analysis, IR, UV/VIS, CD and EPR spectroscopic measurements. Studies by X-ray structure determined and CV are also performed.
By using three-dimensional X-ray diffraction methods, the crystals and molecular structures of the following two complexes have been determined:
（1）[VO(sal-L-val)(μ-O)VO(sal-L-val)(H2O)]
Hexagonal, space group P6, a = 14.5156(7) Å, b = 14.5156(7) Å, c = 45.671(13) Å, V = 8333.7 (8) Å3, Z = 4, R = 0.0824, Rw = 0.1566.
（2）[VO(3-CH3O-sal-L-thr)(H2O)]2(μ-O)
Orthorhombic, space group P21212, a = 18.6587(16) Å, b = 18.9119(16) Å, c = 7.8027(7) Å, V = 2753.4 Å3, Z = 4, R = 0.0694, Rw = 0.1386.
These chiral oxovanadium complexes are utilized in asymmetric sulfoxidation and epoxidation reactions, as shown below. In this studies, we use CD and UV/VIS spectroscopy to determine ee values. This is an efficient determined ee values. In sulfoxidation, the products formed contain mainly (S)-phenyl methyl sulfoxide, while using catalysts having L-aminoacids; and (R)-phenyl methyl sulfoxide is predominant by using catalysts with D-aminoacid. Both [VO(3,5di-t-butyl-sal-L-thr)(L)] and [VO(3,5di-t-butyl-sal-D-val)(L)] result in high yields and enantioselectivites up to 50% ee. A significant improvement in the enantioselectivity was observed while using [VO(5-nitro-sal-L-val)(L)] catalyst.
These vanadium complexes are formed to be poor in epoxidation of allylic alcohols.

並列關鍵字

oxovanadium complexes ； catalyst ； shiff base

參考文獻

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