Computer-aided molecular design of bis-phosphine oxide lanthanide extractants

Billy W. McCann, Nuwan De Silva, Theresa L. Windus, Mark S. Gordon, Bruce A. Moyer, Vyacheslav S. Bryantsev, Benjamin P. Hay

Research output: Contribution to journalArticlepeer-review

46 Scopus citations

Abstract

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 R2(O)P-link-P(O)R2 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 the link is -CH2-, 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.

Original languageEnglish
Pages (from-to)5787-5803
Number of pages17
JournalInorganic Chemistry
Volume55
Issue number12
DOIs
StatePublished - Jun 20 2016

Funding

This work was supported by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The authors thank Drs. Marilu Dick-Perez and Federico Zahariev for helpful discussions.

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