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Issue 37, 2016
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A cobalt(ii) iminoiodane complex and its scandium adduct: mechanistic promiscuity in hydrogen atom abstraction reactions

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Abstract

In addition to oxometal [Mn+[double bond, length as m-dash]O] and imidometal [Mn+[double bond, length as m-dash]NR] units, transient metal–iodosylarene [M(n−2)+–O[double bond, length as m-dash]IPh] and metal–iminoiodane [M(n−2)+–N(R)[double bond, length as m-dash]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.

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

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Publication details

The article was received on 09 May 2016, accepted on 11 Jul 2016 and first published on 14 Jul 2016


Article type: Communication
DOI: 10.1039/C6DT01815G
Dalton Trans., 2016,45, 14538-14543
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    A cobalt(II) iminoiodane complex and its scandium adduct: mechanistic promiscuity in hydrogen atom abstraction reactions

    S. Kundu, P. Chernev, X. Engelmann, C. S. Chung, H. Dau, E. Bill, J. England, W. Nam and K. Ray, Dalton Trans., 2016, 45, 14538
    DOI: 10.1039/C6DT01815G

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