Characterization of the Complexes of Pd(II) of Macrocyclic Diamides Containing Sulfur

• Main Authors: Heng Yi Chen, 陳恒毅
• Other Authors: Lilian
• Format: Others
• Language: zh-TW
• Published: 2000
• Online Access: http://ndltd.ncl.edu.tw/handle/32761789715341138809

碩士 === 國立臺灣師範大學 === 化學研究所 === 88 === Several macrocyclic diamides containing sulfur of various ring sizes were synthesized by modified Hruby and Stocks amide synthesis. They have been used to study the ability of complexation with palladium ion using techniques such as solvent extraction and liquid membrane transport. Results where solvent extraction are good, but liquid membrane transport results are bad are explained by the differences in complex structures. The extraction time can be greatly reduced when stirring is replaced by shaking. Results obtained by shaking 15 min are better or equivalent to those by stirring 210 min at 300 r.p.m. Ligands which have 4 carbons between the two amide groups complexed with Pd（II） in the Pd (II)out-forms. We determine the stability constants（logKs）by using mole-ratio method of UV/Vis spectrometry to complexes of ligands and Pd（II）with hydrochloric acid , and potentiometric titration method to determine the stability constants（logKs） the complexes of Pd（II）with ligands without hydrochloric acid. Two kind of single crystal of the metal-macrocyclic diamide complexes have been obtained and analyzed by single crystal X-ray diffraction. The yellow 4a-in obtained under neutral condition is a tetracoordinated. In which the sulfur and nitrogen atoms in the macrocyclic diamide ring are all coordinated with the Pd (II) ion; due to the deprotonation of the hydrogen on amide group.The red-orange crystal of 4a-out, 3b-out obtained under acidic condition is also a tetracoordinated. In which only the sulfur atoms of the macrocyclic diamide ring are coordinated with the Pd(II) ion.