A pair of trigonal imido iron complexes ([Fe(NMes)L2]0,−) in two oxidation states is reported. The anionic complex K{crypt.222}[Fe(NMes)L2] is best described as an iron(ii) imide.

Carbonyl and iminyl based radical anions are reactive intermediates in a variety of transformations in organic synthesis. Herein, the isolation of ketyl, and more importantly unprecedented ketiminyl and aldiminyl radical anions coordinated to cobalt and iron complexes is presented. Insights into the electronic structure of these unusual metal bound radical anions is provided by X-Ray diffraction analysis, NMR, IR, UV/Vis and Mössbauer spectroscopy, solid and solution state magnetometry, as well as a by a detailed computational analysis. The metal bound radical anions are very reactive and facilitate the activation of intra-and intermolecular CÀ H bonds.

A new salt of the alkylated oxo‐thio stannate cluster [Sn10O4S16(SMe)4]4–, (C4C4C1Im)4[Sn10O4S16(SMe)4] (1), was obtained by ionothermal treatment of K4[SnS4]·4H2O. The reaction was carried out in the ionic liquid 1,3‐dibutyl‐2‐methylimidazolium chloride, (C4C4C1Im)Cl, which proved to be non‐innocent against the chalcogenido metallate species in the reaction mixture. In continuation of our first studies on alkylation of very weakly nucleophilic chalcogenido metalate anions, this study served to prove that an N‐bonded alkyl group is selectively released from the imidazolium cation of the ionic liquid, and it served to show that methylation is favored over butylation. The title compound is one of the rare cases, in which the cations of the salt, which stem from the ionic liquid, could be crystallographically determined without problems.

The molecular compound [BiDipp2(SbF6)], containing the bulky, donor‐free bismuth cation [BiDipp2]+ has been synthesized and fully characterized (Dipp=2,6‐iPr2‐C6H3). Using its methyl analog [BiMe2(SbF6)] as a second reference point, the impact of steric bulk on bismuth‐based Lewis acidity was investigated in a combined experimental (Gutmann‐Beckett and modified Gutmann‐Beckett methods) and theoretical approach (DFT calculations). Reactivity studies of the bismuth cations towards [PF6]− and neutral Lewis bases such as isocyanides C≡NR’ revealed facile fluoride ion abstraction and straightforward Lewis pair formation, respectively. The first examples of compounds featuring bismuth‐bound isocyanides have been isolated and fully characterized.

Bi Lewis acidic: Donor‐free cationic bismuth compounds readily coordinate Lewis basic substrates including arenes, phosphanes, and isonitriles, and degrade the weakly coordinating counter‐anion [PF6]–. Counterintuitively, an increase in steric bulk around bismuth can increase the Lewis acidity. In the graphic, a bismuth kraken grabs Lewis basic substrates, solving scientific puzzles about bismuth‐based Lewis acidity. More information can be found in the Research Article by C. von Hänisch, C. Lichtenberg and co‐workers (DOI: 10.1002/chem.202204012).

Invited for the cover of this issue are the groups of Carsten von Hänisch and Crispin Lichtenberg at the Philipps University of Marburg. The image depicts a bismuth kraken, eagerly grabbing Lewis basic substrates, thereby solving scientific puzzles about bismuth‐based Lewis acidity. Read the full text of the article at 10.1002/chem.202204012.