Organometallics [LCSOM, LECPCS, POMAM]

Abstract :

Recent reports have identified Cp*Co-based complexes to be powerful catalysts for aromatic C–H bond activation under oxidative conditions. However, little is known about the speciation of Cp*Co species during catalysis. We now show that key intermediates, Cp*Co^III metallacycles derived from 2-phenylpyridine (phpy-H), react swiftly in solution with one-electron oxidants to irreversibly collapse by a cyclocondensation of the organic ligands to afford cationic alkaloids in yields of >70%. A low-temperature EPR analysis of a mixture of the cobaltacycle with the tritylium cation reveals the signatures of trityl and Co(IV)-centered radicals. Electrochemical analyses show that the oxidation of these cobaltacycles is irreversible and gives rise to several products in various amounts, among which the most salient ones are a cationic alkaloid resulting from the cyclocondensation of the phpy and Cp* ligands and the dimeric cation {[Cp*Co]₂(μ-I)₃}⁺. DFT investigations of relevant noncovalent interactions using QTAIM-based NCI plots and intrinsic bond strength indexes suggest a ligand-dependent predisposition by “NCI-coding” for the Co(IV)-templated cyclocondensation, the computed reaction network energy profile for which supports the key roles of a short-lived Co(IV) metallacycle and of a range of triplet state organocobalt intermediates.

Graphical Abstract:

 

 
 

Reference :

Fule Wu, Christophe Deraedt, Yann Cornaton, Laurent Ruhlmann, Lydia Karmazin, Corinne Bailly, Nathalie Kyritsakas, Nolwenn Le Breton, Sylvie Choua, Jean-Pierre Djukic

Fate of Cobaltacycles in Cp*Co-Mediated C–H Bond Functionalization Catalysis: Cobaltacycles May Collapse upon Oxidation via Co(IV) Species

Organometallics 2021, 40, 15, 2624–2642. DOI: https://doi.org/10.1021/acs.organomet.1c00301

Contact :

Jean-Pierre Djukic, équipe LCSOM (http://lcsom.u-strasbg.fr), Institut de Chimie (UMR 7177).