Electron‐Transfer Chain Catalysis in Organotransition Metal Chemistry

Abstract

Dedicated to Professor Jean TiroufletParallel to organic electrocatalysis, the field of organotransition metal electrocatalysis has developed explosively since 1980. The theoretical and experimental foundations established by Feldberg in 1971 (ECE mechanism) have been applied, using fast electrochemical techniques, to various organometallic reactions such as isomerization, ligand exchange, chelation, decomplexation, and C O insertion and extrusion. Most of the work performed to date concerns ligand exchange reactions of N-donors and P-donors in mononuclear compounds, initiated by oxidants (or anodes) and of carbonyls and P-donors in clusters, initiated by reducing agents (or cathodes). The preparative aspects of electrocatalysis have already been impressively developed in cluster chemistry and indicate that the technique is extremely useful. This review first delineates the principles and characteristics of electrocatalysis applied in organotransition metal chemistry, and then, after outlining the choice of efficient initiating reagents, goes on to describe the systems up to August 1986.

Synthesis and Some Properties of Bis(ruthenocenyl)thiophene Derivatives – Possible Spin‐Coupling in the Two‐Electron Oxidized Species of Dinuclear Ruthenocenes Bridged by Thiophene Derivatives

“…stability in both the neutral and oxidized forms). [6] Enormous effort has been expended in the synthesis of dinuclear ferrocene derivatives with π-conjugation. [7] In addition, much attention is currently focused on materials that are based on oligothiophenes and polythiophenes because of their re-bridged binuclear ruthenocene derivatives are comparatively stable and adopt the spin-coupled and structurally isomerized fulvene complex-type structure.…”

The Redox Functions of Metallodendrimers

“…In other terms, the catalyst is the carrier of an electron or an electron hole. Electrocatalytic reactions and redox-catalyzed reactions do not necessarily proceed by electrochemistry [113,[123][124][125].…”

“…Finally, the prototypal electron-reservoir complex [Fe(g 5 -C 5 H 5 )(g 6 -C 6 Me 6 )][PF 6 ] stoichiometric and catalytic (redox catalysis, electrocatalysis) in a variety of reactions and processes [54,114,124,125], but it is also a reservoir of 6 or 12 protons in single-pot reactions with a base such as KOH or KOt-Bu and an electrophile such as allylbromide in selective iterative reactions to yield molecular stars (for instance [Fe(g 5 -C 5 H 5 ){g 6 -C 6 {(CH 2 ) 3 (CH = CH 2 )} 6 [145] and dendrimers [146] (e.g. [Fe(g 5 -C 5 H 5 ){g 6 -C 6 {(CH) (CH 2 CH = CH 2 )} 2 } 6 } [147] ).…”

Organometallic Electron-Reservoir Complexes. Concepts and Applications

“…Electron-transfer-chain catalysis, introduced first by Taube and Rich with inorganic complexes, 51 has been much studied and applied to organotransition-metal synthesis in the early 1980s. [52][53][54] The electron-reservoir complexes [Fe…”