NDLI: A TRLFS study on the complexation of novel BTP type ligands with Cm(III)

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Beele, Björn B. Geist, Andreas Panak, Petra J. Müllich, Udo Schwörer, Felicitas Rüdiger, Elias
Description	Author Affiliation: Beele BB ( Ruprecht-Karls-Universität Heidelberg, Institut für Physikalische Chemie, Im Neuenheimer Feld 253, 69120 Heidelberg, Germany. Bjoern.Beele@partner.kit.edu)
Abstract	Two BTP-type N-donor ligands with different numbers of aromatic nitrogen atoms ( 2,6-bis(4-ethyl-pyridazin-1-yl)pyridine , Et-BDP and $2,6-bis(4-^{n}propyl-2,3,5,6-tetrazine-1-yl)pyridine,$ $^{n}Pr-Tetrazine)$ have been synthesized and characterized by NMR and MS techniques. The complexation with Cm(III) in 2-propanol– water (1:1, vol.) is studied for both ligands using time resolved laser-induced fluorescence spectroscopy (TRLFS) and the complexation properties are compared to $^{n}Pr-BTP.$ With increasing the ligand concentration three different species, the 1:1-, 1:2- and 1:3-complex, were found. Log $β_{3}$ values of 7.6 for the formation of $Cm(Et-BDP)_{3}$ and 9.2 for the formation of $Cm(^{n}Pr-Tetrazine)_{3}$ are determined. The complexation with $^{n}Pr-Tetrazine$ shows slow kinetics. Thermodynamic data of the complexation reactions are determined in a temperature range of 25 °C–60 °C. The complexation with Et-BDP is exothermic (ΔH = −16.3 ± 1.2 kJ $mol^{−1})$ and exergonic (ΔG = −43.8 ± 2.6 kJ $mol^{−1})$ whereas the complexation with $^{n}Pr-Tetrazine$ is endothermic (ΔH = 43.9 ± 3.1 kJ $mol^{−1})$ and exergonic (ΔG = −51.7 ± 2.2 kJ $mol^{−1}).$ In the case of the latter the complexation is driven by a highly positive reaction entropy change (ΔS = 320.6 ± 15.4 J $mol^{−1}$ $K^{−1}).$ In comparison to $^{n}Pr-BTP,$ less negative ΔG values were found for the complexation of Cm(III) with both ligands .
ISSN	14779226
Issue Number	34
Journal	Dalton Trans.
Volume Number	42
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-09-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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