Extraction complexes of Pu(IV) with carbamoylmethylphosphine oxide ligands: A relativistic density functional study

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

Research output: Contribution to journalArticle

9 Scopus citations

Abstract

The extraction complexes of Pu(IV) with n-octyl(phenyl)-N,N-diisobutyl- methylcarbamoyl phosphine oxide (CMPO) and diphenyl-N,N-diisobutyl carbamoyl phosphine oxide (Ph2CMPO) have been studied by using density functional theory (DFT) combined with relativistic small-core pseudopotentials. For most complexes, the CMPO and Ph2CMPO molecules are coordinated as bidentate chelating ligands through the carbonyl oxygen and phosphoric oxygen atoms. The metal-ligand bonding is mainly ionic for all of these complexes. The neutral PuL(NO3)4 and PuL2(NO3)4 complexes are predicted to be the most thermodynamically stable molecules according to the metal-ligand complexation reactions. In addition, hydration energies may also play a significant role in the extractability of CMPO and Ph2CMPO for the plutonium cations. In most cases, the complexes with CMPO possess qualitatively similar geometries and electron structures to those with Ph2CMPO, and they also have comparable metal-ligand binding energies. Thus, replacement of alkyl groups by phenyl groups at the phosphorus atomof CMPO seems to have no obvious influence on the extraction of Pu(IV).

Original languageEnglish (US)
Pages (from-to)77-86
Number of pages10
JournalRadiochimica Acta
Volume102
Issue number1-2
DOIs
StatePublished - Feb 2014

Keywords

  • CMPO
  • Ph2 CMPO
  • Plutonium(IV)
  • Relativistic quantum chemistry
  • Solvent extraction

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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