Related Experiment Video
Updated: Jul 12, 2026

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Anodic preparation of [Re2Cp2(CO)6]2+: a dimeric dication that provides the powerful one-electron oxidant
Daesung Chong1, Ayman Nafady, Paulo Jorge Costa
1Department of Chemistry, University of Vermont, Burlington, Vermont 05405, USA.
Abstract:
The half-sandwich piano-stool compounds Re(eta5-C5R5)(CO)3 (1, R = H; or 2, R = Me) are oxidized to the corresponding 17-electron Re(II) cations at glassy carbon anodes in CH2Cl2/[NBu4][B(C6F5)4]. Despite the very strongly positive E1/2 values of the couples (1.16 V for 1/1+ and 0.91 V for 2/2+ vs ferrocene/ferrocenium), the radical cations are persistent in this medium and exist in equilibrium with the corresponding dimeric dications, which may be cathodically reduced back to the neutral starting material. DFT calculations show that the dimer of 1+ achieves its stability through formation of a single long (almost 3.3 A) Re-Re bond made possible when the HOMO in 1 is rehybridized away from the metal in the one-electron oxidation process. The pure salts [1][B(C6F5)4]2 and [2][B(C6F5)4]2 were isolated by preparative anodic electrochemistry. The former may be used for storage of the very strong one-electron oxidant 1+, which was used to prepare a number of oxidation products as their [B(C6F5)4]- salts.
More Related Videos
08:34A Dual-Functional Electroactive Filter Towards Simultaneously Sb(III) Oxidation and Sequestration
Published on: December 5, 2019
10:52Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Related Concept Videos
Redox Reactions
Oxidation-Reduction Reactions
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
Radical Reactivity: Overview
Types of Reversible Electrodes
Redox Reactions