Petit Laurence, Adamo Carlo, Maldivi Pascale
Laboratoire de Reconnaissance Ionique, DRFMC/LCIB (UMR_E 3 CEA-UJF), CEA-Grenoble, 17 rue des Martyrs, F-38054 Grenoble Cedex 9, France.
Inorg Chem. 2006 Oct 16;45(21):8517-22. doi: 10.1021/ic060227g.
Although BTP (2,6-di(1,2,4-triazin-3-yl)pyridine) has been widely evidenced as the most effective nitrogen ligand for the selective complexation of trivalent actinides from lanthanide counterparts, the origin of its selectivity is still an open question. Neither experimental data nor theoretical calculations have been able to rationalize the role of covalency in real experimental BTP complexes. We show herein with DFT calculations on [M(BTP)3]3+ (M = La, U, Cm, Gd) that, even if back-bonding effects are significant in the U-BTP bond, it is the contrast of donation on 6d and 5f Cm(III) orbitals that explains, at least in part, its selective complexation to BTP.
尽管BTP（2,6-二（1,2,4-三嗪-3-基）吡啶）已被广泛证明是从镧系元素对应物中选择性络合三价锕系元素最有效的氮配体，但其选择性的起源仍然是一个悬而未决的问题。无论是实验数据还是理论计算都无法解释共价性在实际实验BTP络合物中的作用。我们在此通过对[M(BTP)3]3+（M = La、U、Cm、Gd）进行密度泛函理论计算表明，即使在U-BTP键中反馈键合效应很显著，但至少部分地解释了其与BTP选择性络合的原因是6d和5f Cm(III)轨道上电子给予的差异。
