Interaction of 6,6′′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2′:6′,2′′-terpyridine (CyMe4-BTTP) with some trivalent ions such as lanthanide(iii) ions and americium(iii)

Abstract

The new ligand 6,6′′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2′:6′,2′′-terpyridine (CyMe₄-BTTP) has been synthesized in 4 steps from 2,2′:6′,2′′-terpyridine. Detailed NMR and mass spectrometry studies indicate that the ligand forms 1 : 2 complexes with lanthanide(III) perchlorates where the aliphatic rings are conformationally constrained whereas 1 : 1 complexes are formed with lanthanide(III) nitrates where the rings are conformationally mobile. An optimized structure of the 1 : 2 solution complex with Yb(III) was obtained from the relative magnitude of the induced paramagnetic shifts. X-Ray crystallographic structures of the ligand and of its 1 : 1 complex with Y(III) were also obtained. The NMR and mass spectra of [Pd(CyMe₄-BTTP)]_n²ⁿ⁺ are consistent with a dinuclear double helical structure (n = 2). In the absence of a phase-modifier, CyMe₄-BTTP in n-octanol showed a maximum distribution coefficient of Am(III) of 0.039 (±20%) and a maximum separation factor of Am(III) over Eu(III) of 12.0 from nitric acid. The metal(III) cations are extracted as the 1 : 1 complex from nitric acid. The generally low distribution coefficients observed compared with the BTBPs arise because the 1 : 1 complex of CyMe₄-BTTP is considerably less hydrophobic than the 1 : 2 complexes formed by the BTBPs. In M(BTTP)³⁺ complexes, there is a competition between the nitrate ions and the ligand for the complexation of the metal.