Electrochemical Oxidation of the Phospha‐ and Arsaethynolate Anions, PCO^– and AsCO^–

Abstract

The anions PCOand AsCOare shown to be electroactive and are studied in aqueous and non-aqueous solutions. Cyclic voltammetry is used to extract fundamental physicochemical parameters such as oxidation peak potentials, and transfer and diffusion coefficients of the anions to better understand the nature of the oxidation process. Variation of the potential scan rate reveals that electro-oxidation of PCOwith the release of CO is controlled by diffusion and is a one-electron [a]

Recent advances in the chemistry of the phosphaethynolate and arsaethynolate anions

“…Compton and Goicoechea et al studied the electrochemical oxidation of the OCP − anion in aqueous solution where they observed that the current increased linearly with the square root of the scan rate in a diffusion-controlled process. 109 Cyclic voltammograms were recorded by varying the potential from 0.0 V to 1.1 V and back to 0.0 V ( vs. an Ag reference) using glassy carbon (GC) as the working electrode (0.1 M KCl), Pt-sponge as the counter electrode and Ag as a pseudo-reference electrode in a deoxygenated solution of 2.0 mm [Na(dioxane) x ](OCP) in 0.1 M KCl. The result was compared with reported irreversible oxidation of [Na(dioxane) x ](OCP) in DMSO containing t Bu 4 NBF 4 as electrolyte.…”