Polyaromatic N-heterocyclic carbene ligands and π-stacking. Catalytic consequences
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Title
Polyaromatic N-heterocyclic carbene ligands and π-stacking. Catalytic consequencesAuthor (s)
Date
2016-04Publisher
Royal Society of ChemistryISSN
1359-7345Bibliographic citation
PERIS, Eduardo. Polyaromatic N-heterocyclic carbene ligands and π-stacking. Catalytic consequences. Chemical Communications, 2016, vol. 52, no 34, p. 5777-5787Type
info:eu-repo/semantics/articleVersion
info:eu-repo/semantics/publishedVersionAbstract
In the course of our most recent research, we demonstrated how homogeneous catalysts with
polyaromatic functionalities possess properties that clearly differ from those shown by analogues lacking
these polyaromatic ... [+]
In the course of our most recent research, we demonstrated how homogeneous catalysts with
polyaromatic functionalities possess properties that clearly differ from those shown by analogues lacking
these polyaromatic systems. The differences arise from the ability of the polyaromatic groups to afford
non-covalent interactions with aromatic molecules, which can either be substrates in a homogeneous
catalysed reaction, or the same catalysts to afford self-assembled systems. This article summarizes all
our efforts toward understanding the fundamental effects of p-stacking interactions in homogenous
catalysis, particularly in those cases where catalysts bearing polyaromatic functionalities are used. The
study reveals several important implications regarding the influence of ligand–ligand interactions,
ligand–additive interactions, and ligand–substrate interactions, in the performance of the catalysts used.
In particular, the electronic properties of ligands with fused polyconjugated systems, are modified if
molecules with p-stacking abilities are added, via a ligand–additive interaction. Also, the kinetics of the
reactions in which aromatic substrates and catalysts with polyaromatic ligands are used, are strongly
influenced by the self-association of the catalysts and by the non-covalent interaction between the
catalyst and the aromatic substrates. The nature and the magnitude of these supramolecular interactions
were unveiled by using host–guest chemistry methods applied to organometallic catalysis. Finally, noncovalent
interactions afford a very convenient approach for the immobilization of catalysts decorated
with polyaromatic systems onto the surfaces of graphene derivatives, hence affording an easy yet
extremely effective way to support catalysts and facilitate recycling. The results given have fundamental
implications in the design of future catalysts containing rigid polyaromatic systems, and may inspire
future researchers in the design of improved homogeneous catalysts, by taking into account that the
activities of the metal complexes are strongly modified by supramolecular interactions. [-]
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Chemical Communications, 2016, 52, p. 5777-5787Rights
This journal is © The Royal Society of Chemistry 2016
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