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A cobalt(II) iminoiodane complex and its scandium adduct: mechanistic promiscuity in hydrogen atom abstraction reactions

Title
A cobalt(II) iminoiodane complex and its scandium adduct: mechanistic promiscuity in hydrogen atom abstraction reactions
Authors
Kundu, SubrataChernev, PetkoEngelmann, XeniaChung, Chan SiuDau, HolgerBill, EckhardEngland, JasonNam, WonwooRay, Kallol
Ewha Authors
남원우
SCOPUS Author ID
남원우scopus
Issue Date
2016
Journal Title
DALTON TRANSACTIONS
ISSN
1477-9226JCR Link1477-9234JCR Link
Citation
vol. 45, no. 37, pp. 14538 - 14543
Publisher
ROYAL SOC CHEMISTRY
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
In addition to oxometal [Mn+=O] and imidometal [Mn+=NR] units, transient metal-iodosylarene [M(n- 2)+-O=IPh] and metal-iminoiodane [M(n- 2)+-N(R)=IPh] adducts are often invoked as a possible "second oxidant" responsible for the oxo and imido group transfer reactivity. Although a few metal-iodosylarene adducts have been recently isolated and/or spectroscopically characterized, metal-iminoiodane adducts have remained elusive. Herein, we provide UV-Vis, EPR, NMR, XAS and DFT evidence supporting the formation of a metal-iminoiodane complex 2 and its scandium adduct 2-Sc. 2 and 2-Sc are reactive toward substrates in the hydrogen-atom and nitrene transfer reactions, which confirm their potential as active oxidants in metal-catalyzed oxidative transformations. Oxidation of para-substituted 2,6-di-tert-butylphenols by 2 and 2-Sc can occur by both coupled and uncoupled proton and electron transfer mechanisms; the exact mechanism depends on the nature of the para substituent.
DOI
10.1039/c6dt01815g
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자연과학대학 > 화학·나노과학전공 > Journal papers
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