Stable meso-meso-Linked 2NH-Corrole Radical Dimers as a Key Intermediate to Corrole Tape.
Angew Chem Int Ed Engl
; 59(24): 9423-9427, 2020 Jun 08.
Article
em En
| MEDLINE
| ID: mdl-32170827
ABSTRACT
While oxidation of 5,5',15,15'-tetramesityl-10-10'-linked 3NH-corrole dimer with DDQ gave the corresponding triply linked 2NH-corrole tape, the use of an equimolar amount of p-chloranil as a milder oxidant resulted in the formation of a 10-10'-linked neutral 2NH-corrole radical dimer as a stable product. The stability of this peculiar product is ascribed largely to strong antiferromagnetic interaction of the two spins. Further oxidation of this diradical produced corrole tape, suggesting its involvement as a reaction intermediate to the corrole tape. Oxidation of 10-10'-linked bis-pyridine-coordinated CoIII corrole dimer with DDQ produced a cobalt corrole radical dimer and a doubly linked corrole dimer both as stable compounds bearing pyridine and cyanide axial ligands. This type of oxidative transformation involving neutral diradical intermediates is a unique reaction mechanism specific for corrole dimers.
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01-internacional
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MEDLINE
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En
Ano de publicação:
2020
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Article