α‐Metallated ylides have revealed themselves to be versatile reagents for the introduction of ylide groups. Herein, we report the synthesis of the thiophosphinoyl and piperidyl (Pip) substituted α‐metallated ylide [Ph 2 (Pip)P=C−P(S)Ph 2 ]M (M=Li, Na, K) through a four‐step synthetic procedure starting from diphenylmethylphosphine sulfide. Metallation of the ylide intermediate was successfully accomplished with different alkali metal bases delivering the lithium, sodium and potassium salts, the latter isolable in high yields. Structure analyses of the lithium and potassium compounds in the solid state with and without crown ether revealed different aggregates (monomer, dimer and hexamer) with the metals coordinated by the thiophosphoryl moiety and ylidic carbon atom. Although the piperidyl group does not coordinate to the metal, it significantly contributes to the stability of the yldiide by charge delocalization through negative hyperconjugation.

The use of well-defined palladium(II) complexes as precatalysts for C-X cross-coupling reactions has improved the use of palladium catalysts in organic synthesis including large scale processes. Whereas sophisticated Pd(II) precursors...

The synthesis and structure analysis of a series of mono and diylide‐substituted tetrylenes of type YEX and Y2E (E=Ge, Sn, Pb; X=Cl or Br) using a thiophosphinoyl‐tethered metallated ylide (Y=Ph2P(S)−C−P(pip)Ph2 with pip=piperidyl) is reported, amongst the first ylide‐substituted plumbylenes. The tetrylenes feature distinct trends in the spectroscopic and structural properties of the ylide ligand with increasing atomic number of the tetrel element. For instance, an increasingly high‐field shifted signal for the thiophosphinoyl group is observed in the 31P{1H} NMR spectrum as a consequence of the increasing polarity of the element‐carbon bond, which likewise results in a shortening of the ylidic C−P bond in the solid‐state structure. The diylidyltetrylenes are unstable towards transylidation forming the mono(ylide)tetrylenes when treated with the tetrel dihalides according to the stability trend: Y2Pb

Invited for this month's cover is the group of Viktoria H. Gessner at the Ruhr‐University in Bochum (Germany). The cover shows the structure of the newly reported, isolated metallated ylide. Due to the high negative charge at the ylidic carbon center this compound is „on fire“, but can be stabilized by smart molecular design. Structure analyses of the different alkali metal complexes combined with computational studies provide insights into the electronic structure of the compounds Read the full text of their Communication at 10.1002/open.202100187.

The Front Cover shows the structure of the newly reported, isolated metallated ylide. Due to the high negative charge at the ylidic carbon center this compound is „on fire“, but can be stabilized by smart molecular design. Structure analyses of the different alkali metal complexes combined with computational studies provide insights into the electronic structure of the compounds. More information can be found in the Communication by by Mike Jörges et al.