How Metal Ion Lewis Acidity and Steric Properties Influence the Barrier to Dioxygen Binding, Peroxo O-O Bond Cleavage, and Reactivity was written by Yan Poon, Penny Chaau;Dedushko, Maksym A.;Sun, Xianru;Yang, Guang;Toledo, Santiago;Hayes, Ellen C.;Johansen, Audra;Piquette, Marc C.;Rees, Julian A.;Stoll, Stefan;Rybak-Akimova, Elena;Kovacs, Julie A.. And the article was included in Journal of the American Chemical Society in 2019.Recommanded Product: (6-Methoxypyridin-2-yl)methanol This article mentions the following:
Herein we quant. investigate how metal ion Lewis acidity and steric properties influence the kinetics and thermodn. of dioxygen binding vs. release from structurally analogous Mn-O2 complexes, as well as the barrier to Mn peroxo O-O bond cleavage, and the reactivity of Mn oxo intermediates. Previously we demonstrated that the steric and electronic properties of MnIII-OOR complexes containing N-heterocyclic (NAr) ligand scaffolds can have a dramatic influence on alkylperoxo O-O bond lengths and the barrier to alkylperoxo O-O bond cleavage. Herein, we examine the dioxygen reactivity of a new MnII complex containing a more electron-rich, less sterically demanding NAr ligand scaffold, and compare it with previously reported MnII complexes. Dioxygen binding is shown to be reversible with complexes containing the more electron-rich metal ions. The kinetic barrier to O2 binding and peroxo O-O bond cleavage is shown to correlate with redox potentials, as well as the steric properties of the supporting NAr ligands. The reaction landscape for the dioxygen chem. of the more electron-rich complexes is shown to be relatively flat. A total of four intermediates, including a superoxo and peroxo species, are observed with the most electron-rich complex. Two new intermediates are shown to form following the peroxo, which are capable of cleaving strong X-H bonds. In the absence of a sacrificial H atom donor, solvent, or ligand, serves as a source of H atoms. With TEMPOH as sacrificial H atom donor, a deuterium isotope effect is observed (kH/kD = 3.5), implicating a hydrogen atom transfer (HAT) mechanism. With 1,4-cyclohexadiene, 0.5 equiv of benzene is produced prior to the formation of an EPR detected MnIIIMnIV bimetallic species, and 0.5 equiv after its formation. In the experiment, the researchers used many compounds, for example, (6-Methoxypyridin-2-yl)methanol (cas: 63071-12-5Recommanded Product: (6-Methoxypyridin-2-yl)methanol).
(6-Methoxypyridin-2-yl)methanol (cas: 63071-12-5) belongs to ethers. Relative to alcohols, ethers are generally less dense, are less soluble in water, and have lower boiling points. They are relatively unreactive, and as a result they are useful as solvents for fats, oils, waxes, perfumes, resins, dyes, gums, and hydrocarbons. Vapours of certain ethers are used as insecticides, miticides, and fumigants for soil. Electron-deficient reagents are also stabilized by ethers. For example, borane (BH3) is a useful reagent for making alcohols. Pure borane exists as its dimer, diborane (B2H6), a toxic gas that is inconvenient and hazardous to use. Borane forms stable complexes with ethers, however, and it is often supplied and used as its liquid complex with tetrahydrofuran (THF).Recommanded Product: (6-Methoxypyridin-2-yl)methanol
Referemce:
Ether – Wikipedia,
Ether | (C2H5)2O – PubChem