In the rising field of organoindium chemistry little is known about the perfluoroorganyl‐substituted indium compounds. The increasing use of indium reagents is explained by their high stability and tolerance towards water and functional groups. Here we report on the synthesis of the novel tetrakis(pentafluoroethyl)indate, [In(C2F5)4]−, and its characterization in salts with the cations [Li(thf)3]+, Cs+, [PPh4]+ and [H14O6]2+ (thf=tetrahydrofuran). To the best of our knowledge, these salts constitute the first perfluoroalkylindates and, in general, the first isolated perfluoroalkylindium compounds which are fully characterized by NMR spectroscopy, mass spectrometry, elemental analysis and X‐ray diffraction analysis.

We report on the molecular structure of trimethylsilanes Si(CH3)3X in which the substituents X, namely (Z)‐pentafluoropropen‐1‐yl, trifluoropropyn‐1‐yl, pentafluoroethyl, trifluorovinyl, vinyl, propyn‐1‐yl, di‐ and trichloromethyl, display electron withdrawing effects of varying strength. The lengths of the bonds between the silicon and the carbon atoms of X correlate with the hybridization of the respective orbitals and the steric demand of X rather than with the electron withdrawing capability. In case of chlorinated substituents dispersion effects seem to shorten the Si−C bond. Furthermore, a route for generating trifluoropropyn‐1‐yllithium from the cryogen 2,3,3,3‐tetrafluoropropene (HFO‐1234yf) and n‐butyllithium is described. Tetrafluoropropen‐1‐yllithium is slowly formed at −80 °C but even at this temperature spontaneous elimination of LiF occurs. Deprotonation of the formed 3,3,3‐trifluoropropyne requires temperatures of above −60 °C leading to trifluoropropyn‐1‐yllithium which appears as relatively stable at room temperature.

The Front Cover shows a series of trimethylsilanes Si(CH3)3X that were structurally characterized. The selected silanes are useful tools for the transfer of the functional groups X. Herein X represents electron withdrawing alkyl, alkenyl, and alkynyl groups containing hydrogen or electronegative fluorine or chlorine atoms. The silanes are easily prepared from the respective lithium reagent LiX and chlorotrimethylsilane. A new route for the preparation of LiX (X = trifluoropropyn‐1‐yl) starting from the cryogen 2,3,3,3‐tetrafluoropropene was discovered. More information can be found in the Full Paper by B. Hoge and co‐workers.