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Issue 9, 2003
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The coordination chemistry of 1,2,4-triazinyl bipyridines with lanthanide(iii) elements – implications for the partitioning of americium(iii)

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Abstract

It has been established that 6-(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2′-bipyridines (R,hemi-BTPs) have properties which are intermediate between those of the terpyridines and the bis(1,2,4-triazin-3-yl)pyridines (BTPs). However, they resemble the terpyridines much more closely than the BTPs. It has been shown that Et,hemi-BTP when dissolved in TPH—a dodecane-like solvent—is a selective reagent for the separation of americium(III) from europium(III). Solution NMR in acetonitrile largely confirmed the crystallographic results. There was no evidence for a 1 ∶ 3 complex cation, or for significant differences between metal(III)–N distances for the pyridine and 1,2,4-triazine rings. Intramolecular hydrogen bonding plays a crucial role in the formation of metal coordination spheres, which explains the differences between the terpyridyl, R,hemi-BTPs and the BTPs. Protonation of the R,hemi-BTPs facilitates a conformational change which is necessary for complexation.

Graphical abstract: The coordination chemistry of 1,2,4-triazinyl bipyridines with lanthanide(iii) elements – implications for the partitioning of americium(iii)

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Article information


Submitted
29 Jan 2003
Accepted
25 Mar 2003
First published
07 Apr 2003

Dalton Trans., 2003, 1675-1685
Article type
Paper

The coordination chemistry of 1,2,4-triazinyl bipyridines with lanthanide(III) elements – implications for the partitioning of americium(III)

M. J. Hudson, M. G. B. Drew, M. R. StJ. Foreman, C. Hill, N. Huet, C. Madic and T. G. A. Youngs, Dalton Trans., 2003, 1675
DOI: 10.1039/B301178J

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