%0 Journal Article
%A McCann, Billy W.
%A Silva, Nuwan
De
%A Windus, Theresa L.
%A Gordon, Mark S.
%A Moyer, Bruce A.
%A Bryantsev, Vyacheslav S.
%A Hay, Benjamin P.
%D 2016
%T Computer-Aided Molecular Design of Bis-phosphine Oxide
Lanthanide Extractants
%U https://acs.figshare.com/articles/journal_contribution/Computer_Aided_Molecular_Design_of_Bis_phosphine_Oxide_Lanthanide_Extractants/2252452
%R 10.1021/acs.inorgchem.5b02995.s001
%2 https://acs.figshare.com/ndownloader/files/3888412
%K R 2
%K host architectures
%K ligand geometry
%K ligand structures
%K screening millions
%K design approach
%K trivalent lanthanides
%K CH
%K earth elements
%K novel ligands
%K Molecule building software
%K oxide
%K lanthanide complexation
%K steric origin
%K mechanics software
%X 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.
%I ACS Publications