Issue 9, 2020

Peroxocobalt(iii) species activates nitriles via a superoxocobalt(ii) diradical state

Abstract

The dioxygenation of nitriles by [CoIII(TBDAP)(O2)]+ (TBDAP = N,N-di-tert-butyl-2,11-diaza[3.3](2,6)-pyridinophane) is investigated using DFT-calculations. The mechanism proposed previously based on experimental observations, which invoked an outer-sphere cycloaddition, was found to be unreasonable. Instead, calculations suggest that an inner-sphere mechanism involving the cleavage of one of the Co–O bonds assisted by substrate uptake is much more likely. The reactively competent species is a triplet consisting of a Co(II)-superoxo functionality, which can undergo O–C bond formation and O–O bond cleavage traversing low energy transition states. The role of the structurally rigid TBDAP ligand is to prevent the participation of the pyridyl ligand in the delocalization of the unpaired electron density.

Graphical abstract: Peroxocobalt(iii) species activates nitriles via a superoxocobalt(ii) diradical state

Supplementary files

Article information

Article type
Paper
Submitted
25 ربيع الأول 1441
Accepted
14 جمادى الأولى 1441
First published
15 جمادى الأولى 1441

Dalton Trans., 2020,49, 2819-2826

Peroxocobalt(III) species activates nitriles via a superoxocobalt(II) diradical state

D. Cho, S. Choi, J. Cho and M. Baik, Dalton Trans., 2020, 49, 2819 DOI: 10.1039/D0DT00042F

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