Theoretical investigation on the elusive biomimetic iron(III)-iodosylarene chemistry: An unusual hydride transfer triggers the Ritter reaction

Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme CoIII(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds

“…Activation energies for the conversion of 1 LBHB and 1′ LBHB to 2 are as large as 26.2 and 26.0 kcal mol –1 , and the endothermicities are 23.6 and 24.7 kcal mol –1 , respectively. The conversion of the cobalt–iodosylarene species 1 LBHB and 1′ LBHB to the cobalt–oxyl species 2 is not feasible both kinetically and thermodynamically, like some other metal–iodosylarene/iodylarene complexes. − Thus, due to the oxo-wall proposed by Gray and co-workers, ,− only 1 LBHB and 1′ LBHB are left as the potential oxidants for styrene oxidation by 1 in the presence of HOTf.…”

The elusive active species in nickel(ii)-mediated oxidations of hydrocarbons by peracids: a NiII–oxyl species, an aroyloxy radical, or a NiII–peracid complex?

“…60,63 Thus, Ni II -mediated oxidation of cyclohexane with mCPBA proceeds via a multipleoxidant scenario. [64][65][66][67] These mechanistic findings enrich the knowledge of peracid activation by transition metals after group 8 in periodic table of elements and will play a positive role in rational design of new catalysts.…”

Which is the real oxidant in competitive ligand self-hydroxylation and substrate oxidation—a biomimetic iron(ii)-hydroperoxo species or an oxo-iron(iv)-hydroxy one?

“…[19][20][21][22][23][24][25] So far, extensive mechanis-tic studies have been generally carried out on the synthetic nonheme iron(II) complexes with artificial oxidants such as iodosylarenes, peroxides and peroxy acids. 1,[26][27][28][29][30][31][32][33][34] Dioxygen, a green and economically friendly oxidizing agent, is used as an effective terminal oxidant in the whole biosphere and has received wide attention in bioinspired chemistry. Inspired by Nature, Que, Paine and their co-workers have revealed that the suicide cofactor, α-keto or α-hydroxy acid, can promote the dioxygen activation mediated by a mononuclear non-heme iron(II) complex to complete the following oxidation reactions (Scheme 1).…”

“…19–25 So far, extensive mechanistic studies have been generally carried out on the synthetic nonheme iron( ii ) complexes with artificial oxidants such as iodosylarenes, peroxides and peroxy acids. 1,26–34…”