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

Subrata Kundu, Petko Chernev, Xenia Engelmann, Chan Siu Chung, Holger Dau, Eckhard Bill, Jason England, Wonwoo Nam, Kallol Ray

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

In addition to oxometal [Mn+O] and imidometal [Mn+NR] units, transient metal-iodosylarene [M(n-2)+-OIPh] 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.

Original languageEnglish
Pages (from-to)14538-14543
Number of pages6
JournalDalton Transactions
Volume45
Issue number37
DOIs
StatePublished - 2016

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