Complexation behavior of Eu(III) and Am(III) with CMPO and Ph 2CMPO ligands: Insights from density functional theory

Cong Zhi Wang, Wei Qun Shi, Jian Hui Lan, Yu Liang Zhao, Yue Zhou Wei, Zhi Fang Chai

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45 Scopus citations


A series of extraction complexes of Eu(III) and Am(III) with CMPO (n-octyl(phenyl)-N,N-diisobutyl-methylcarbamoyl phosphine oxide) and its derivative Ph2CMPO (diphenyl-N,N-diisobutyl carbamoyl phosphine oxide) have been studied using density functional theory (DFT). It has been found that for the neutral complexes of 2:1 and 3:1 (ligand/metal) stoichiometry, CMPO and Ph2CMPO predominantly coordinate with metal cations through the phosphoric oxygen atoms. Eu(III) and Am(III) prefer to form the neutral 2:1 and 3:1 type complexes in nitrate-rich acid solutions, and in the extraction process the reactions of [M(NO3)(H2O) 7]2+ + 2NO3 - + nL → ML n(NO3)3 + 7H2O (M = Eu, Am; n = 2, 3) are the dominant complexation reactions. In addition, CMPO and Ph 2CMPO show similar extractability properties. Taking into account the solvation effects, the metal-ligand binding energies are obviously decreased, i.e., the presence of solvent may have an significant effect on the extraction behavior of Eu(III) and Am(III) with CMPOs. Moreover, these CMPOs reagents have comparable extractability for Eu(III) and Am(III), confirming that these extractants have little lanthanide/actinide selectivity in acidic media.

Original languageEnglish (US)
Pages (from-to)10904-10911
Number of pages8
JournalInorganic Chemistry
Issue number19
StatePublished - Oct 7 2013

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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