Synlett 2023; 34(10): 1169-1173
cluster
Dispersion Effects
Activation Barriers for Cobalt(IV)-Centered Reductive Elimination Correlate with Quantified Interatomic Noncovalent Interactions
Lucas Loir-Mongazon
,
Carmen Antuña-Hörlein
,
Christophe Deraedt
,
Yann Cornaton∗
,
Centre national de la Recherche Scientifique, University of Strasbourg, GENCI-IDRIS grant 2021-A0100812469, the HPC Center of the University of Strasbourg grant g2021a248c.
Abstract
In this joint theoretical and experimental study, an analysis of weak interligand noncovalent interactions within Co(IV) [Cp*Co(phpy )X]+ cobaltacycles (phpy = 2-phenylenepyridine, κ
C ,N
) was carried out by using the independent gradient model/intrinsic bond strength index (IGM/IBSI) method to evaluate the dependency of the catalytically desired reductive elimination pathway (RE) on the nature of the X ligand. It is shown that the barrier for activation of the RE pathway correlates directly with the IBSI of the X-to-carbanionic chelate’s carbon. This correlation suggests that in silico prediction of which X ligand is more prone to operate an efficient Cp*Co-catalyzed directed X-functionalization of an aromatic C–H bond is attainable. A set of experiments involving various sources of X ligands supported the theoretical conclusions.
Key words
metallacycles -
cobalt catalysis -
density functional theory -
noncovalent interactions -
reductive elimination -
C–H bond activation
Publication History
Received: 13 July 2022
© 2022. Thieme. All rights reserved
Georg Thieme Verlag KG
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