ic5b02995_si_001.pdf (2.4 MB)
Computer-Aided Molecular Design of Bis-phosphine Oxide Lanthanide Extractants
journal contribution
posted on 2016-02-16, 19:56 authored by Billy W. McCann, Nuwan
De Silva, Theresa L. Windus, Mark S. Gordon, Bruce A. Moyer, Vyacheslav S. Bryantsev, Benjamin P. HayComputer-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.