cr8b00588_si_002.pdf (166.12 kB)
Computational Ligand Descriptors for Catalyst Design
Version 2 2019-03-08, 20:35
Version 1 2019-02-25, 20:49
journal contribution
posted on 2019-02-25, 00:00 authored by Derek
J. Durand, Natalie FeyLigands,
especially phosphines and carbenes, can play a key role
in modifying and controlling homogeneous organometallic catalysts,
and they often provide a convenient approach to fine-tuning the performance
of known catalysts. The measurable outcomes of such catalyst modifications
(yields, rates, selectivity) can be set into context by establishing
their relationship to steric and electronic descriptors of ligand
properties, and such models can guide the discovery, optimization,
and design of catalysts. In this review we present a survey of calculated
ligand descriptors, with a particular focus on homogeneous organometallic
catalysis. A range of different approaches to calculating steric and
electronic parameters are set out and compared, and we have collected
descriptors for a range of representative ligand sets, including 30
monodentate phosphorus(III) donor ligands, 23 bidentate P,P-donor
ligands, and 30 carbenes, with a view to providing a useful resource
for analysis to practitioners. In addition, several case studies of
applications of such descriptors, covering both maps and models, have
been reviewed, illustrating how descriptor-led studies of catalysis
can inform experiments and highlighting good practice for model comparison
and evaluation.