DIOXYGEN ACTIVATION · Dioxygen activation by copper in an inert cage
6РП — Действия „Мария Кюри“
- Период
- 2007-02-01 → 2009-01-31
- Финансиране от ЕС
- 148 588 €
- Участници
- 1
- Схема
- EIF
Линиите свързват координатора с партньорите.
Накратко на български
Метални комплекси в специални молекулярни „клетки“ се използват за активиране на кислорода чрез мед. Тези процеси помагат за разработването на нови флуоресцентни биологични сонди и фотосенсибилизатори.
Кратко обяснение, генерирано от езиков модел по текста на CORDIS. Оригиналът е по-долу.
Резултати накратко
Final Activity Report Summary - DIOXYGEN ACTIVATION (Dioxygen activation by copper in an inert cage)
Polytopic ligands in which three bidentate (2,2'-bipyridine or catechol) units are linked to a central tris(pyrid-2-yl)amine or tris(pyrid-2-yl)methanol moiety by alkyl spacers were prepared by multistep organic syntheses. The parent tris(pyrid-2-yl) type ligands were shown to be modest to good chelators for Zn2+ and Cu2+ ions in solution. The structural metals FeII and RuII (in case of 2,2'-bipyridine) and FeIII (in case of catechol) smoothly form stable, cage-like 1:1 complexes with the ligands in which the metal ion is coordinated to the tris(bidentate) site. The vacant tris(pyrid-2-yl) site of these complexes is, however, a poor donor site for Zn2+ and Cu2+ ions. Therefore, the structural metals (FeII, FeIII and RuII) might be considered as allosteric effectors which modulates the metal binding properties of the second tris(pyrid-2-yl) site of the ligands. Contrary to expectation, Zn2+ and Cu2+ appear to associate weakly with donor atoms directed toward the exterior of the cage-like complexes, rather than locating in the interior of the container by tripodal coordination to the tris(pyrid-2-yl) site. Consequently, studies on the dioxygen activation by the copper complexes were complicated low metal ion affinity of the container. The synthesis of fluorinated analogs was also attempted, however, stability of amide and imine linkage was found to be rather poor against solvolysis, probably due to the strong electron withdrawing effect of the perfluoro substituents. In parallel, functionalised fluorescent (bpy)3Ru2+ complexes which lack the second, tris(pyrid-2-yl) binding site were synthesised. Their selective binding to specific target molecules was evaluated. New fluorescent biological probes has been developed and the light-induced activation of dioxygen (photosensitised generation of singlet oxygen) has been shown in living cells.
Текст от CORDIS, на английски · Данни: CORDIS, © Европейски съюз
Цел на проекта
The aim of the project is to design and synthesize a new type of low-molecular-weight single Cu site which smoothly converts organic substrates to oxidised/oxygenated products in the presence of benign oxidants O2 or H2O2. In particular, the copper site is located at the bottom of a chemically inert cage, which should enhance the lifetime of a Cu(I)-O2 adduct at room temperature and prevent intra-molecular oxygenation of the ligand, but at the same time favours reaction with substrates by their incorporation in the cavity and exposure to the activated O2 species.These systems are believed to be ideal models for a study of the properties and reactivity of monocopper-oxygen species, and potentially new reagents or catalyst for selective oxidations/oxygenations including less reactive hydrocarbon substrates (arenes, alkenes, alkanes). Since the covalent synthesis of such an encaged copper centre would be rather challenging, the metal-based assembly of the cage from a tripodal precursor and an allosteric, second metal ion is suggested, to obtain the target ligand readily and in sufficient quantity for thorough investigations including screening of reactivity.
Оригинален текст от CORDIS (на английски).
Участници
- RUPRECHT-KARLS-UNIVERSITÄT HEIDELBERG · HEIDELBERGКоординаторГермания
Връзки
Данни: CORDIS, © Европейски съюз