A cobalt(ii) iminoiodane complex and its scandium adduct: mechanistic promiscuity in hydrogen atom abstraction reactions. Issue 37 (28th July 2016)

• Record Type: Journal Article
• Authors: Kundu, Subrata; Chernev, Petko; Engelmann, Xenia; Chung, Chan Siu; Dau, Holger; Bill, Eckhard; England, Jason; Nam, Wonwoo; Ray, Kallol
• Is Part Of: Dalton transactions. Volume 45:Issue 37(2016)
• Page Start: 14538
• Page End: 14543
• Publication Date: 2016-07-28
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt01815g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : In addition to imidometal [M n + NR] units, transient metal–iminoiodane [M ( n −2)+ −N(R)IPh] adducts have been demonstrated as a possible "second oxidant" responsible for the imido group transfer reactivity. Abstract : In addition to oxometal [M n + O] and imidometal [M n + 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 complex2 and its scandium adduct2-Sc .2 and2-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 by2 and2-Sc can occur by both coupled and uncoupled proton and electron transfer mechanisms; the exact mechanism depends on the nature of the para substituent.