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

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• 作者：Billy W. McCann ; Nuwan De Silva ; Theresa L. Windus ; Mark S. Gordon ; Bruce A. Moyer ; Vyacheslav S. Bryantsev ; Benjamin P. Hay
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：June 20, 2016
• 年：2016
• 卷：55
• 期：12
• 页码：5787-5803
• 全文大小：799K
• 年卷期：0
• ISSN：1520-510X

文摘

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<sub>2sub>(O)P–link–P(O)R<sub>2sub> 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 −CH<sub>2sub>–, 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.