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

Date
2016-06-20
Authors
Windus, Theresa
Gordon, Mark
Windus, Theresa L.
Gordon, Mark S.
Moyer, Bruce A.
Bryantsev, Vyacheslav S.
Hay, Benjamin P.
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American Chemical Society
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Chemistry
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Ames Laboratory
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ChemistryAmes Laboratory
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.
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This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Inorganic Chemistry, copyright © 2016 American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acs.inorgchem.5b02995. Posted with permission.
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Computer-aided molecular design, bis-phosphine oxide, organophosphorus extractant, anomalous aryl strengthening effect, rare earth elements, lanthanides, B3LYP, MM3, HostDesigner
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