Cited 0 time in webofscience Cited 0 time in scopus

Distinct Reactivity of a Mononuclear Peroxocobalt(III) Species toward Activation of Nitriles

Title
Distinct Reactivity of a Mononuclear Peroxocobalt(III) Species toward Activation of Nitriles
Authors
Noh, HyeonjuJeong, DonghyunOhta, TakehiroOgura, TakashiValentine, Joan SelverstoneCho, Jaeheung
DGIST Authors
Jeong, Donghyun; Cho, Jaeheung
Issue Date
2017
Citation
Journal of the American Chemical Society, 139(32), 10960-10963
Type
Article
Article Type
Article
Keywords
Activation AnalysisAmbient ConditionsChemical ActivationCobalt CompoundsConcerted MechanismCrystallographyCyanidesHammett AnalysisIsotope Labeling ExperimentsLigandsOverall ReactionsPeroxo LigandsSpectroscopic TechniqueTetradentate MacrocyclicX Ray Crystallography
ISSN
0002-7863
Abstract
A mononuclear side-on peroxocobalt(III) complex with a tetradentate macrocyclic ligand, [CoIII(TBDAP)(O2)]+ (1), shows a novel and facile mode of dioxygenase-like reactivity with nitriles (R - C=N; R = Me, Et, and Ph) to produce the corresponding mononuclear hydroximatocobalt(III) complexes, [CoIII(TBDAP)(R - C(=NO)O)]+, in which the nitrile moiety is oxidized by two oxygen atoms of the peroxo group. The overall reaction proceeds in one-pot under ambient conditions (ca. 1 h, 40 °C). 18O-Labeling experiments confirm that both oxygen atoms are derived from the peroxo ligand. The structures of all products, hydroximatocobalt(III) complexes, were confirmed by X-ray crystallography and various spectroscopic techniques. Kinetic studies including the Hammett analysis and isotope labeling experiments suggest that the mechanistic mode of 1 for activation of nitriles occurs via a concerted mechanism. This novel reaction would be significantly valuable for expanding the chemistry for nitrile activation and utilization. © 2017 American Chemical Society.
URI
http://hdl.handle.net/20.500.11750/4413
DOI
10.1021/jacs.7b04479
Publisher
American Chemical Society
Files:
There are no files associated with this item.
Collection:
Emerging Materials ScienceETC1. Journal Articles


qrcode mendeley

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

BROWSE