Issue 37, 2016

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

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

Supplementary files

Article information

Article type
Communication
Submitted
09 mai 2016
Accepted
11 jul 2016
First published
14 jul 2016
This article is Open Access
Creative Commons BY license

Dalton Trans., 2016,45, 14538-14543

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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