The field of multimetallic catalysis is rapidly developing and some multimetallic complexes catalyze organic transformations to yield the desired products in more efficient ways owing to the combined action of different metals in a cooperative fashion. This Concept article describes the recent advances of cooperative catalysis playing in multimetallic systems such as homo-multimetallic complexes with short metal-metal distances, homo-multimetallic complexes with long metal-metal distances, hetero-multimetallic complexes and metallocenebased multimetallic complexes with special attention towards redox-switchable catalysis. Examples are illustrated in which the use of multimetallic complexes show clear enhancement of catalytic outcomes when compared with the sum of their corresponding mononuclear counterparts. Furthermore, several examples are discussed showing the effects of electronic communication in cooperative systems.

Virtually inert sulfur hexafluoride becomes a precious pentafluorosulfanylation agent, if properly activated by photoredox catalysis, to access α-fluoro and αalkoxy SF 5 -compounds. This advanced protocol converts SF 6 in the presence of alkynols as bifunctional CÀ C-and CÀ Obond forming reagents directly into pentafluorosulfanylated oxygen-containing heterocycles in a single step from α-substituted alkenes. The proposed mechanism is supported by theoretical calculations and gives insights not only in the pentafluorosulfanylation step but also into formation of the carbon-carbon bond and is in full agreement with Baldwin's cyclization rules. The key step is a radical type 5-, 6-respectively 7-exo-dig-cyclization. The synthesized oxaheterocycles cannot be simply prepared by other synthetic methods, show a high level of structural complexity and significantly expand the scope of pentafluorosulfanylated building blocks valuable for medicinal and material chemistry.

A retro‐style arcade machine needs an oxidant or a proton to be inserted to start playing and to switch the donating capabilities of novel phosphine ligands orthogonally and reversibly. Rh‐catalysed hydrosilylation showed that these triggers can influence either the rate of conversion and/or the product distribution. The Japanese kanji for “iron” highlights the ferrocene moiety in the ligands′ metal complexes. More information can be found in the Communication by F. Dielmann, F. Breher et al. (DOI: 10.1002/chem.202101969).

A series of redox‐responsive ferrocenyl‐substituted boranes and boronic esters were synthesized. Oxidation of the ferrocenyl ligand to the ferrocenium resulted in a drastic increase in the Lewis acidity beyond the strength of SbF5, which was investigated experimentally and computationally. The resulting highly Lewis acidic boron compounds were used for catalytic C−F and S−F bond activation.

Novel multistimuli-responsive phosphine ligands comprising a redox-active [3]dioxaphosphaferrocenophane backbone and a P-bound imidazolin-2-ylidenamino entity that allows switching by protonation are reported. Investigation of the corresponding metal complexes and their redox behaviour are reported and show the sensitivity of the system towards protonation and metal coordination. The experimental findings are supported by DFT calculations. Protonation and oxidation events are applied in Rhcatalysed hydrosilylations and demonstrate a remarkable influence on reactivity and/or selectivity.