Features of the oxidation of certain hydroxy derivatives of ferrocene with molecular oxygen in organic solvents

The generation of α‐ferrocenyl carbocations from ferrocenyl alcohols for SN1 substitution at the water–organic solvent interface is initiated by the transfer of protons into the organic phase. The proton flux, and hence the reaction rate, can be controlled by addition of a suitable “phase‐transfer catalyst” anion or by external polarization with a potentiostat, providing a new method for the synthesis of ferrocene derivatives.

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Electrochemically Controlled Proton‐Transfer‐Catalyzed Reactions at Liquid–Liquid Interfaces: Nucleophilic Substitution on Ferrocene Methanol

Peljo

Qiao

Murtomäki

et al. 2012

ChemPhysChem

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Peroxide-Selective Reduction of O₂ at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide

et al. 2022

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Metal peroxides are key species involved in a range of critical biological and synthetic processes. Rare-earth (group III and the lanthanides; Sc, Y, La−Lu) peroxides have been implicated as reactive intermediates in catalysis; however, reactivity studies of isolated, structurally characterized rare-earth peroxides have been limited. Herein, we report the peroxide-selective (93−99% O 2 2-) reduction of dioxygen (O 2 ) at redox-inactive rare-earth triflates in methanol using a mild metallocene reductant, decamethylferrocene (Fc*). The first molecular praseodymium peroxide ([Pr III 2 (O 2 2−)-(18C6) 2 (EG) 2 ][OTf] 4 ; 18C6 = 18-crown-6, EG = ethylene glycol, − OTf = − O 3 SCF 3 ; 2-Pr) was isolated and characterized by singlecrystal X-ray diffraction, Raman spectroscopy, and NMR spectroscopy. 2-Pr displays high thermal stability (120 °C, 50 mTorr), is protonated by mild organic acids [pK a1 (MeOH) = 5.09 ± 0.23], and engages in electrophilic (e.g., oxygen atom transfer) and nucleophilic (e.g., phosphate-ester cleavage) reactivity. Our mechanistic studies reveal that the rate of oxygen reduction is dictated by metal-ion accessibility, rather than Lewis acidity, and suggest new opportunities for differentiated reactivity of redox-inactive metal ions by leveraging weak metal−ligand binding events preceding electron transfer.

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Features of Ferrocenylcarboxic Acid Protonation with Brønsted Acids

Фомин

Shuklina

Klimova

2020

Russ. J. Phys. Chem.

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Features of the oxidation of certain hydroxy derivatives of ferrocene with molecular oxygen in organic solvents

Cited by 5 publications

References 11 publications

Electrochemically Controlled Proton‐Transfer‐Catalyzed Reactions at Liquid–Liquid Interfaces: Nucleophilic Substitution on Ferrocene Methanol

Electrochemically Controlled Proton‐Transfer‐Catalyzed Reactions at Liquid–Liquid Interfaces: Nucleophilic Substitution on Ferrocene Methanol

Peroxide-Selective Reduction of O₂ at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide

Features of Ferrocenylcarboxic Acid Protonation with Brønsted Acids

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Features of the oxidation of certain hydroxy derivatives of ferrocene with molecular oxygen in organic solvents

Cited by 5 publications

References 11 publications

Electrochemically Controlled Proton‐Transfer‐Catalyzed Reactions at Liquid–Liquid Interfaces: Nucleophilic Substitution on Ferrocene Methanol

Electrochemically Controlled Proton‐Transfer‐Catalyzed Reactions at Liquid–Liquid Interfaces: Nucleophilic Substitution on Ferrocene Methanol

Peroxide-Selective Reduction of O2 at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide

Features of Ferrocenylcarboxic Acid Protonation with Brønsted Acids

Contact Info

Product

Resources

About

Peroxide-Selective Reduction of O₂ at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide