1 |
Synthesis and Characterization of Metal Complexes Derived from a Trisphenolato Phosphine LigandSu, Wei-jia 15 July 2008 (has links)
We utilized the tripodal ligand (tris-(3,5-di-tert-butyl-2-hydroxy-phenyl)- phosphine) H3[O3P] to react with 1 equiv of AlR3 (R = Cl, Me, Et, iBu and OiPr). From NMR and X-ray data proved, we could give the stable Al(III) complexes [O3P-H]AlR (R = Cl, Me, Et and iBu). [O3P-H]AlR is a zwitterionic complexes. Because the phenolato phosphine ligand bond a proton at the phosphorous, and Al(III) coordinated three RO- (tris phenolate group) and one alkyl- substituent group. So the Al(III) metal could be carried -1 charge and the phosphorous could be carried +1 charge. When H3[O3P] reacted with AlR3, the original trisphenolato phosphine ligand ([O3P]3-) was changed into a trisphenoato phosphonium ligand ([O3P-H]2-).
The [O3P-H]AlMe in the trisphenoato phosphonium group has a proton, and we attempted to use a bese to deprotonate the acidic proton. We chose n-BuLi to react with [O3P-H]AlMe, and successfully gave {[O3P:]AlMe}- ionic complexe. In the {[O3P:]AlMe}- complexe, the lone pair electron of phenolato phosphine group is a nucleophile,It reacted with MeOTf of electrophile. The product of the reaction could give [O3P-Me]AlMe.In this reactions, the original trisphenoato phosphonium ligand ([O3P-H]2-) was changed into a new methyl trisphenoato phosphonium ligand ([O3P-Me]2-). We could utilize H3[O3P] to react with 1 equiv MeOTf in diethyl ether, and gave a new tripodal ligand {H3[O3P-Me]}OTf. Also, we utilized the {H3[O3P-Me]}OTf to react with 1 equiv of AlR3 (R = Cl, Me, Et and iBu). We gave that Al(III) complexes [O3P-Me]AlR (R = Cl, Me, Et and iBu).
|
2 |
Syntheses and Characterization of 4-(Di(2-pyridymethyl)-aminomethyl)imidazolyl Metal (Zn, Cu, Ni, Fe) ComplexesLin, Jing-Hung 11 August 2005 (has links)
Late transition metal complexes bearing nitrogen-containing ligands have many applications in biotechnology or industrial catalysis. Imidazole is one of the most common biofunctional ligands to play critical roles in meta1loenzymes, since the imidazole moiety of the histidyl residues often constitutes all or part of the binding sites of various transition metal ions.
We use the newly synthesized tetradentate ligand containing the imidazolyl and pyridyl functional group to react with zinc, copper, nickel, and iron ions in order to carry out biomimetic studies. We have obtained two crystal structures via different methods of crystallization. One of them is a mononuclear complex while the other is a polymeric structure. The polymeric structure has demonstrated the spontaneous deprotonation on the imidazolyl nitrogen on binding to the metal ion followed by the intermolecular self-assembly process.We believe that the imidazolate -bridged complexes undergo the pH-dependent interconversions between mononuclear (protonated ligand) and self-assembled oligomer (deprotonated ligand). In addition, we have measured the titration curves of the tetradentate ligand and its corresponding metal complexes to determine the preferential binding sites at varying pH. From the titration processes, we got the protonation constant of ligand and stability constants of its corresponding metal complexes.
|
Page generated in 0.0792 seconds