Supporting Electrolyte Effects in Electrochemistry: Copper and Mercury Acetylacetonates in Acetonitrile Solvent

Abstract

The anodic mercury wave of acetylacetonate and the reduction of normalCufalse(normalacac)2 have been investigated in acetonitrile solvent. The electrochemistry of both species is substantially modified by the presence of lithium perchlorate in the tetraethylammonium perchlorate supporting electrolyte. The anodic mercury wave of acetylacetonate yields a stable mercury (II) acetylacetonate product in lithium‐containing medium; the product complex undergoes rapid decomposition in the absence of lithium. A coordinative interaction of lithium ion with normalHgfalse(normalacac)2 is postulated. The reduction of normalCufalse(normalacac)2 proceeds in a single two electron wave in Et4NClO4 electrolyte and in two single electron steps in LiClO4‐Et4NClO4 electrolyte. An interpretation resting on the instability of normalCufalse(normalacac)2− and the coordination of acetylacetonate by lithium ion, to give Li2false(normalacac)+ , is given to account for this behavior.

Spectroelectrochemistry of Vanadium Acetylacetonate and Chromium Acetylacetonate for Symmetric Nonaqueous Flow Batteries

“…22 When the nonaqueous electrochemistry of Cr(acac) 3 was compared between Hg and Pt working electrodes, experiments using Hg suggested the presence of three distinct reduction events, whereas those with Pt only indicated one. 17 The Cr(acac) 3 complex oxidizes at relatively high potentials, which have only been * Electrochemical Society Student Member.…”

“…3,21 Most reports of Cr(acac) 3 electrochemistry describe experiments performed with Hg electrodes, which have been observed to form complexes with acac -ions. 22 When the nonaqueous electrochemistry of Cr(acac) 3 was compared between Hg and Pt working electrodes, experiments using Hg suggested the presence of three distinct reduction events, whereas those with Pt only indicated one. 17 The Cr(acac) 3 complex oxidizes at relatively high potentials, which have only been probed with solid electrodes because they are beyond the oxidation potential of Hg.…”

Electrodeposition of uranium in dimethyl sulfoxide and its inhibition by acetylacetone as studied by EQCM

“…The relationship of such potentials of reduction waves and Hacac concentrations was formerly discussed on Fe(III) and Cu(II) in the AN [16,17]. In these studies, coordination species with one, two and more acetylacetonate ligands were produced with increasing the Hacac concentration.…”

Visible-Light-Driven Hydrogen Peroxide Synthesis by a Hybrid Photocatalyst Consisting of Bismuth Vanadate and Bis(hexafluoroacetylacetonato)copper(II) Complex

“…The present system possesses the selectivity of 2e – ORR much higher than Au/TiO 2 ( n = 1.6) and Au/BiVO 4 ( n = 2.5) (requirement 2) . A small reduction wave is observed at −0.3 V, which was not observed in the measurements using the glassy carbon electrode in a previous study . Presently, the origin is unclear, and further investigation is needed to elucidate the detailed reduction mechanism.…”

“…35 A small reduction wave is observed at −0.3 V, which was not observed in the measurements using the glassy carbon electrode in a previous study. 36 Presently, the origin is unclear, and further investigation is needed to elucidate the detailed reduction mechanism.…”