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Title: Computer-Aided Molecular Design of Bis-phosphine Oxide Lanthanide Extractants

Computer-aided molecular design and high-throughput screening of viable host architectures can significantly reduce the efforts in the design of novel ligands for efficient extraction of rare earth elements. This paper presents a computational approach to the deliberate design of bis-phosphine oxide host architectures that are structurally organized for complexation of trivalent lanthanides. Molecule building software, HostDesigner, was interfaced with molecular mechanics software, PCModel, providing a tool for generating and screening millions of potential R 2(O)P-link-P(O)R 2 ligand geometries. The molecular mechanics ranking of ligand structures is consistent with both the solution-phase free energies of complexation obtained with density functional theory and the performance of known bis-phosphine oxide extractants. For the case where link is -CH 2-, evaluation of the ligand geometry provides the first characterization of a steric origin for the ‘anomalous aryl strengthening’ effect. The design approach has identified a number of novel bis-phosphine oxide ligands that are better organized for lanthanide complexation than previously studied examples.
 [1] ;  [2] ;  [2] ;  [2] ;  [1] ;  [1] ;  [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
  3. Supramolecular Design Inst., Oak Ridge, TN (United States)
Publication Date:
Report Number(s):
Journal ID: ISSN 0020-1669
Grant/Contract Number:
AC02-07CH11358; AC02-05CH11231; AC05-00OR22725
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; Journal Issue: 12; Journal ID: ISSN 0020-1669
American Chemical Society (ACS)
Research Org:
Ames Laboratory (AMES), Ames, IA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
Work for Others (WFO); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Advanced Manufacturing Office (EE-5A); USDOE Office of Science (SC)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Computer-aided molecular design; bis-phosphine oxide; organophosphorus extractant; anomalous aryl strengthening effect; rare earth elements; lanthanides; B3LYP; MM3; HostDesigner
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1327587