Journal
SYNLETT
Volume 34, Issue 10, Pages 1169-1173Publisher
GEORG THIEME VERLAG KG
DOI: 10.1055/a-1937-9296
Keywords
metallacycles; cobalt catalysis; density functional theory; noncovalent interactions; reductive elimination; C-H bond activation
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In this study, a combination of theoretical and experimental approaches was used to analyze weak interligand noncovalent interactions in Co(IV) [Cp*Co(phpy)X](+) cobaltacycles. The independent gradient model/intrinsic bond strength index (IGM/IBSI) method was employed to evaluate the dependence of the catalytically desired reductive elimination pathway (RE) on the nature of the X ligand. The results showed that the barrier for activation of the RE pathway is directly correlated with the IBSI of the X-to-carbanionic chelate's carbon, indicating the possibility of in silico prediction of efficient Cp*Co-catalyzed directed X-functionalization of an aromatic C-H bond based on X ligand properties. Experimental evidence supported the theoretical conclusions.
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, kappa(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.
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