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

Kundu, S., Chernev, P., Engelmann, X. , Chung, C.S., Dau, H., Bill, E., England, Jason, Nam, W. and Ray, K. (2016) A cobalt(ii) iminoiodane complex and its scandium adduct: Mechanistic promiscuity in hydrogen atom abstraction reactions. Dalton Transactions, 45 (37). pp. 14538-14543. ISSN 1477-9226

Full content URL: https://doi.org/10.1039/C6DT01815G

Full text not available from this repository.

Item Type:Article
Item Status:Live Archive

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. © 2016 The Royal Society of Chemistry.

Keywords:Atoms, Cobalt compounds, Electron transitions, Metals, Oxidants, Scandium, Electron transfer mechanisms, Group transfer, Hydrogen atom abstraction, Hydrogen atoms, Metal-catalyzed, Oxidative transformations, Transfer reaction, Transient metal, Scandium compounds
Subjects:F Physical Sciences > F120 Inorganic Chemistry
Divisions:College of Science > School of Chemistry
ID Code:51902
Deposited On:11 Oct 2022 10:17

Repository Staff Only: item control page