Organometallic catalysis under visible light activation is an emerging field. Activation by photosensitization or by direct light absorption of organometallic complexes can facilitate or trigger elementary steps in a catalytic cycle such as pre-catalyst reduction, oxidative addition, transmetalation and reductive elimination, as well as the ability of generating radical intermediates, widening the structural diversity offered by classical couplings. This perspective aims to highlight key examples of these light-induced or enhanced processes, with an emphasis on the underlying mechanisms involved.

Less than ten years of acquaintance with hypercoordinated silicon derivatives in our lab is described in this account. Martin's spirosilane derivatives open new opportunities as ligands and as agents for the activation of small molecules and bis‐catecholato silicates have proven to be exquisite radical precursors in photoredox conditions for broad synthetic applications.

This minireview provides an overview of the synthesized bis(catecholato)silicates based on the nature of the alkyl or aryl residues and associated cations as well as the methods developed for this purpose. Structural and analytical data such as the 29Si NMR shift of silicon penta‐ and hexacoordinate derivatives, selected examples of crystal structures by X‐ray diffraction analysis and oxidation potentials of silicates are reported. Some aspects of reactivity are also mentioned.

Metal-catalyzed alkylation of 1,1-dihalovinyl moiety commonly suffers from both a lack of stereoselectivity and the overreaction leading to the dialkylation product. The methodology described herein features a new pathway to alkylate stereoselectively β,β-dichloro-styryl substrates to provide the (Z)-trisubstituted olefin only with fair to good yields. This cross-coupling reaction bears on the smooth and photo-induced formation of a C-centered radical that engages in a nickel-catalyzed organometallic cycle to form the key Csp2-Csp3 bond.

We herein report the first synthesis of a Martin silicate bearing a pentafluoroethyl chain. The full characterisation of this new pentacoordinated silicon species is detailed. Insights on its electronic properties based on structural, physicochemical and computational data are provided. A comparative study of reactivity in solution and in solid state by mechanochemistry has been performed in order to assess the ability of this bench‐stable salt to act as a safe C2F5‐alkylation reagent in a nucleophilic or radical manner.