Complexes formed between the quadridentate, heterocyclic molecules 6,6′-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and lanthanides(iii): implications for the partitioning of actinides(iii) and lanthanides(iii)

Abstract

New hydrophobic, tetradentate nitrogen heterocyclic reagents, 6,6′-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2′-bipyridines (BTBPs) have been synthesised. These reagents form complexes with lanthanides and crystal structures with 11 different lanthanides have been determined. The majority of the structures show the lanthanide to be 10-coordinate with stoichiometry [Ln(BTBP)(NO₃)₃] although Yb and Lu are 9-coordinate in complexes with stoichiometry [Ln(BTBP)(NO₃)₂(H₂O)](NO₃). In these complexes the BTBP ligands are tetradentate and planar with donor nitrogens mutually cisi.e. in the cis, cis, cis conformation. Crystal structures of two free molecules, namely C2-BTBP and CyMe₄-BTBP have also been determined and show different conformations described as cis, trans, cis and trans, trans, trans respectively. A NMR titration between lanthanum nitrate and C5-BTBP showed that two different complexes are to be found in solution, namely [La(C5-BTBP)₂]³⁺ and [La(C5-BTBP)(NO₃)₃]. The BTBPs dissolved in octanol were able to extract Am(III) and Eu(III) from 1 M nitric acid with large separation factors.