From Electron‐Reservoir Complexes to Dendritic Molecular Nanobatteries

Abstract

In this review, which is mostly focused on the concepts and work developed in the author's laboratory, the access and properties of electron-reservoir (redox-robust) transition-metal complexes with sufficiently negative redox potentials and their branching to the tethers of dendrimers and other related nanodevices are highlighted, with the idea of designing dendritic molecular batteries.

Ligand Redox Non‐Innocence in Transition‐Metal σ‐Alkynyl and Related Complexes

“…In addition, many common reaction mechanisms (e.g., oxidative addition, reductive elimination) are described in terms of formal two-electron redox state changes at a metal centre. The capacity for metal complexes to accommodate such a variable number of electrons has led to interest in these systems as electron reservoirs [1,2] and mono-or multi-electron redox reagents, [3,4] and accounts for the wide-spread application of metal complexes in the catalytic transformations of organic substrates through oxidative or reductive coupling charge and spin density can be tuned from being largely metal-centred to alkynyl ligand-centred by variation of the nature of the metal, supporting ligands and alkynyl substituents. This review summarises the diverse chemical behaviour of metal-supported σ-alkynyl radicals, and some selected closely related systems, which can often be rationalised in terms of the distribution of electron-spin density over the metal-alkynyl scaffold.…”