Characterization and reactivity study of non-heme high-valent iron–hydroxo complexes

Abstract

A terminal FeIIIOH complex, [FeIII(L)(OH]2– (1), has been synthesized and structurally characterized (H4L = 1,2-bis(2-hydroxy-2-methylpropanamido)benzene). The oxidation reaction of 1 with one equiv. of tris(4-bromophenyl)ammoniumyl hexachloroantimonate (TBAH) or ceric ammonium...

Electrocatalytic Water Oxidation Activity of Molecular Copper Complexes: Effect of Redox-Active Ligands

“…In a recent study, Zhang and co-workers suggested the formation of ligand radical-coordinated cobalt­(III) complexes supported by a tetra-amido-macrocyclic ligand (TAML) during WO . We also recently characterized a ligand radical-coordinated iron­(III) complex, [Fe III (L 1 •+ )]­(OH)] − . Formation of such a ligand radical species likely stimulates the electrophilic nature of the copper­(III) center for further reaction with OH – .…”

A Metal–Organic Framework as a Multiphoton Excitation Regulator for the Activation of Inert C(sp3)−H Bonds and Oxygen

“…Thesmall but significant CeÀObond difference between Ce À OEt of about 2.44 and Ce À OH 2 of 2.55 in average suggests that the coordinated alcohol is deprotonated. [13] Twoi dentical Ce III ions are bridged by carboxylic groups from four different ligands to constitute the unique dinuclear Ce 2 secondary building unit as af our-point connected node for undulating monolayer (Figures 1b and S2). Each deprotonated NAD + ligand acts as at wo-point connected node to connect two different Ce 2 units with two bidentate carboxylic groups and one monodentate oxygencoordinated carboxylic group,constructing athree-dimension porous framework with the shortest Ce•••N (NAD + )s eparation of approximately 5.59 (Figure 1b), which is beneficial for the synergy of two active sites between the NAD + fragments and Ce À OEt moieties inside the metal-organic framework skeleton structure.…”

Oxidative versus basic asynchronous hydrogen atom transfer reactions of Mn(iii)-hydroxo and Mn(iii)-aqua complexes

“…Mechanisms of hydrogen atom transfer (HAT) reactions from organic substrates (SH) to metal-oxygen complexes, such as metal-oxo, metal-hydroxo, [24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39] metal-(hydro)peroxo [40][41][42][43][44] and metal-superoxo, [45][46][47][48][49][50][51][52][53][54] have been investigated extensively, as summarized in Scheme 1. HAT proceeds via the transfer of both a proton and an electron which can be transferred simul-spectrum of "asynchronicity", in which the transition state for the HAT reaction can contain either more PT or more ET character (Scheme 1).…”

“…Mechanisms of hydrogen atom transfer (HAT) reactions from organic substrates (SH) to metal–oxygen complexes, such as metal-oxo, 1–23 metal-hydroxo, 24–39 metal-(hydro)peroxo 40–44 and metal-superoxo, 45–54 have been investigated extensively, as summarized in Scheme 1. HAT proceeds via the transfer of both a proton and an electron which can be transferred simultaneously in a coupled fashion (concerted proton–electron transfer, CPET) or a stepwise fashion (proton transfer–electron transfer, PT/ET, or electron transfer–proton transfer, ET/PT) (Scheme 1).…”