Redefining the Mechanistic Scenario of Carbon−Sulfur Nucleophilic Coupling via High‐Valent Cp*Co<sup>IV</sup> Species

López‐Resano, Sara; Salinas, Sara Martı́nez de; Garcés‐Pineda, Felipe A.; Moneo‐Corcuera, Andrea; Galán‐Mascarós, José Ramón; Maseras, Feliu; Pérez‐Temprano, Mónica H.

doi:10.1002/ange.202101390

Cited by 3 publications

(3 citation statements)

References 43 publications

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“…159 A detailed mechanistic study by Maseras, Pérez-Temprano, and co-workers revealed the involvement of a Cp*Co(IV) species in the reductive elimination step of this transformation. 160 An oxidant-free thiolation of indoles using N -(arylthio)succinimides was reported by the Anbarasan group. 161…”

Section: C–h Activationmentioning

confidence: 99%

Recent Metal-Catalyzed Methods for Thioether Synthesis

et al. 2022

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This review summarizes the more recent methods for the synthesis of thioethers using homogeneous metals as catalysts. The thioether moiety can be found in numerous compounds for pharmaceutical, agricultural or material applications and it is therefore important to develop new, efficient methods for their synthesis. The recent efforts in this field focus on the use of non-precious metal catalysts, as well as on the development of new bond-forming processes. 1 Introduction 2 Cross-couplings 3 C-H Activation 4 Hydrothiolation 5 Carbothiolation 6 Miscelaneous 7 Conclusion

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Section: C–h Activationmentioning

confidence: 99%

Recent Metal-Catalyzed Methods for Thioether Synthesis

et al. 2022

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“…Indeed, two recent studies 9 have outlined the central role of highly reactive transient Co(IV) metallacycles in C–H bond functionalization (Scheme 1 ), revealing that the nature of the X ligand, often introduced to functionalize the aromatic C–H bond, 10 is crucial. 9b Such Co(IV)–reactant complexes might indeed evolve by at least two main pathways: (1) the reductive elimination 9a (RE) desired in catalysis 10 or (2) the undesired collapse 9b of the key Cp*Co motif by a cyclocondensation (CC) of the carbanionic chelating ligand with the Cp* ligand (Scheme 1 ).…”

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confidence: 99%

“…Previous studies suggested that the oxidation of the Co(III) complex I to a Co(IV) [ I ] + is required to trigger the RE. 9a To clarify whether or not this oxidation is mandatory, the RE activation energies at the Co(III) and Co(IV) states were compared. Note that, whereas the Co(IV) transition states were readily located by using a simple linear transit procedure, the Co(III) ones required more-careful exploration of the potential-energy surface.…”

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Activation Barriers for Cobalt(IV)-Centered Reductive Elimination Correlate with Quantified Interatomic Noncovalent Interactions

LOIR-MONGAZON

Antuña-Hörlein

Deraedt

et al. 2022

Synlett

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In this joint theoretical and experimental study, the analysis of weak interligand noncovalent interactions within Co(IV) [Cp*Co(phpy)X]+ cobaltacycles (phpy = 2-phenylenepyridine, κC,N) was carried out using the 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 of activation of the RE pathway correlates directly with the IBSI of the X-to-carbanionic chelate’s carbon. This correlation suggests that the in silico prediction of which -X ligand is more prone to operate an efficient Cp*Co-catalyzed directed X-functionalization of aromatic C-H bond is at reach. A set of experiments staging various sources of -X ligands supports the theoretical conclusions.

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Cobalt Nanoparticles Formed upon Reaction of Cp*Co(III) Metallacycles with Na[BHEt₃] Show Catalytic Activity in the Hydrosilylation of Aryl Ketones, Aldehydes and Nitriles

Antuña-Hörlein

Deraedt

et al. 2022

Eur J Inorg Chem

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The reactivity of the 2-phenylpyridine-derived [Cp*CoI(phpyk C,N )] metallacycle towards Et 3 SiH and hydrides was evaluated. The treatment of the same Co(III) complex with Na[BHEt 3 ] resulted in its decomposition into cobalt nanoparticles. The hydride-promoted decomposition of the metallacycle involves the transient formation of an elusive hydrido-cobalt(III) intermediate, the traces of which were detected by 1 H NMR spectroscopy at sub-ambient temperature. The Co nanoparticles produced from a 5 mol% and 10 mol% load of cobaltacycle and Na[BHEt 3 ] respectively contain Co(0) that is responsible for the hydrosilylation by Et 3 SiH of arylketones into silylalkyl ethers. To minimize the residual side reduction of carbonyls by Na[BHEt 3 ], a mixture of 5 mol% of the latter with 5 mol% of BEt 3 was found to produce optimal hydrosilylation yields at 40 °C in 2 h. Under similar conditions, several arylnitriles were mono-hydrosilylated into N-silyl-imines in yields ranging from 68 to 100 %.

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Redefining the Mechanistic Scenario of Carbon−Sulfur Nucleophilic Coupling via High‐Valent Cp*Co^IV Species

Cited by 3 publications

References 43 publications

Recent Metal-Catalyzed Methods for Thioether Synthesis

Recent Metal-Catalyzed Methods for Thioether Synthesis

Activation Barriers for Cobalt(IV)-Centered Reductive Elimination Correlate with Quantified Interatomic Noncovalent Interactions

Cobalt Nanoparticles Formed upon Reaction of Cp*Co(III) Metallacycles with Na[BHEt₃] Show Catalytic Activity in the Hydrosilylation of Aryl Ketones, Aldehydes and Nitriles

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Redefining the Mechanistic Scenario of Carbon−Sulfur Nucleophilic Coupling via High‐Valent Cp*CoIV Species

Cited by 3 publications

References 43 publications

Recent Metal-Catalyzed Methods for Thioether Synthesis

Recent Metal-Catalyzed Methods for Thioether Synthesis

Activation Barriers for Cobalt(IV)-Centered Reductive Elimination Correlate with Quantified Interatomic Noncovalent Interactions

Cobalt Nanoparticles Formed upon Reaction of Cp*Co(III) Metallacycles with Na[BHEt3] Show Catalytic Activity in the Hydrosilylation of Aryl Ketones, Aldehydes and Nitriles

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Redefining the Mechanistic Scenario of Carbon−Sulfur Nucleophilic Coupling via High‐Valent Cp*Co^IV Species

Cobalt Nanoparticles Formed upon Reaction of Cp*Co(III) Metallacycles with Na[BHEt₃] Show Catalytic Activity in the Hydrosilylation of Aryl Ketones, Aldehydes and Nitriles