Non-Fe Metal Complexes with a Siderophore Inspired Chelate
| Autor: | Chrisman, Mark A. |
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| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: | |
| Druh dokumentu: | Text |
| Popis: | The coordination chemistry and photochemistry of the X-Sal-AHA chelates has been expanded from FeIII to other metals. New gallium and uranium complexes have been synthesized with the X-Sal-AHA chelate series. The structures of the gallium complexes are nearly identical to those of the Fe Sal-AHA complexes previously synthesized. These complexes share a trinuclear structure with M3O4 incomplete cubane cores. The main difference between the complexes is that while the iron complex underwent a decarboxylation when irradiated the gallium trimer was not photoactive. Given the similarities in the structures, mixed iron-gallium complexes were synthesized to study the effect that different amounts of iron present in the trimer would have on the photochemistry. The uraniumcomplex shows a doubly anionic dimeric structure in which each metal is coordinated in a pentagonal bipyramidal geometry. This is quite different from the pseudo-octahedral geometry seen with the iron and gallium complexes. Although the overall shape of the uranium complex is very different, there are similarities in chelate binding. Each ligand binds two metal centers with the salicylidene portion binding one metal and the carboxylate binding the second metal with the hydroxyl group bridging the two metals. When the uranyl complex was irradiated it gave the same initial photoproduct from the chelate as the iron complexes. This photoproduct was an aldehyde formed after the decarboxylation of the chelate. The photochemistry of the uranyl Sal-AHA complexes is more similar to the iron Sal-AHA complexes than usual uranyl photochemistry in which it is known for its oxidizing ability. |
| Databáze: | Networked Digital Library of Theses & Dissertations |
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