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

Title
Peroxocobalt(III) species activates nitriles via a superoxocobalt(II) diradical state
Authors
Cho, DasolChoi, SeulhuiCho, JaeheungBaik, Mu-Hyun
DGIST Authors
Cho, Dasol; Choi, Seulhui; Cho, Jaeheung; Baik, Mu-Hyun
Issue Date
2020-03
Citation
Dalton Transactions, 49(9), 2819-2826
Type
Article
Article Type
Article
Keywords
SOLVATION FREE-ENERGIESH BOND ACTIVATIONSPECTROSCOPIC CHARACTERIZATIONMOLECULAR CALCULATIONSELECTRONIC-STRUCTUREHYDROGEN-PEROXIDEAEROBIC OXIDATIONCOMPLEXREACTIVITYMECHANISM
ISSN
1477-9226
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. This journal is © The Royal Society of Chemistry.
URI
http://hdl.handle.net/20.500.11750/11787
DOI
10.1039/d0dt00042f
Publisher
Royal Society of Chemistry
Files:
There are no files associated with this item.
Collection:
Department of Emerging Materials ScienceBiomimetic Materials Laboratory1. Journal Articles


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