Interactions of CyMe4‐BTBP ligand with lanthanides and actinides: Insights from ESI‐MS and DFT calculations

Electrospray Ionization Mass Spectrometry (ESI‐MS) technique and density functional theory (DFT) calculations were combined to study the formation of the complexes of lanthanides (Ln = La, Ce, Nd, Sm, Eu, Yb) and actinides (UO22+, Th4+) with CyMe4‐BTBP (6,6′‐bis(5,5,8,8‐tetramethyl‐5,6,7,8‐tetrahydro‐benzo‐[1,2,4‐]triazin‐3‐yl)‐[2,2′]bipyridine) to understand the mechanisms during the extraction process. Mass spectrometry titrations showed the formation of the complexation in acetonitrile. For lanthanides, only 1:2 complexes ([Ln(L)2]3+, [Ln(L)2(CH3CN)]3+), [Ln(L)2(NO3)]2+) were found at low [Ln]/[L] concentration ratios, whereas the 1:1 complexes ([Ln(L)(NO3)2]+) were observed when the [Ln]/[L] concentration ratio reached 1.0. For uranyl complexes, 1:1 complex ([UO2L(NO3)]+) was the only species within the measuring range. Th4+ complexes had two compositions: 1:1 and 1:2, in which 1:2 species was the dominant complex. Collision‐induced dissociation (CID) was employed to characterize the fragmentation process. The fragmentation process was unfolded sequentially on both sides of CyMe4‐BTBP ligand with the loss of alkyl groups and cleavage of triazinyl rings. The CID results of CyMe4‐BTBP complexes revealed a slight difference depending on the metal center. The DFT calculations showed that the stable complexes formed in acetonitrile solution were consistent with the ESI‐MS results.