Correction to “Correlating Reactivity and Selectivity to Cyclopentadienyl Ligand Properties in Rh(III)-Catalyzed C–H Activation Reactions: An Experimental and Computational Study”

Recent reports have identified Cp*Co-based complexes as 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 %. Low temperature EPR analysis of a mixture of cobaltacycle with the tritylium cation reveals the signatures of trityl and Co(IV)-centred 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 (-I) 3 } + . DFT investigations of relevant noncovalent interactions using QTAIMbased NCI plots and Intrinsic Bond Strength Index 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. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service www.ccdc.cam.ac.uk/structures. Full experimental procedures and details, voltammograms, EPR, Mass and NMR spectra, energies and Cartesian coordinates, high resolution NCI figures. This material is available free of charge via the Internet at http://pubs.acs.org.

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Correction to “Correlating Reactivity and Selectivity to Cyclopentadienyl Ligand Properties in Rh(III)-Catalyzed C–H Activation Reactions: An Experimental and Computational Study”

Cited by 3 publications

References 1 publication

Rhodium(II)‐Catalyzed C(sp³)−H Diamination of Arylcyclobutanes

Rhodium(II)‐Catalyzed C(sp³)−H Diamination of Arylcyclobutanes

Rhodium(II)‐Catalyzed C(sp³)−H Diamination of Arylcyclobutanes

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

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Correction to “Correlating Reactivity and Selectivity to Cyclopentadienyl Ligand Properties in Rh(III)-Catalyzed C–H Activation Reactions: An Experimental and Computational Study”

Cited by 3 publications

References 1 publication

Rhodium(II)‐Catalyzed C(sp3)−H Diamination of Arylcyclobutanes

Rhodium(II)‐Catalyzed C(sp3)−H Diamination of Arylcyclobutanes

Rhodium(II)‐Catalyzed C(sp3)−H Diamination of Arylcyclobutanes

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

Contact Info

Product

Resources

About

Rhodium(II)‐Catalyzed C(sp³)−H Diamination of Arylcyclobutanes

Rhodium(II)‐Catalyzed C(sp³)−H Diamination of Arylcyclobutanes

Rhodium(II)‐Catalyzed C(sp³)−H Diamination of Arylcyclobutanes