The 7-membered cyclic thionolactone, ε-thionocaprolactone (TCL), undergoes radical copolymerization with vinyl esters to form degradable copolymers. While most radical ring-opening monomers require laborious and low-yielding syntheses, TCL can be prepared in one step from caprolactone (75% yield). TCL copolymerizes readily with vinyl esters, but is unreactive towards more activated monomers and does not homopolymerize under radical conditions. The molecular weight and to some extent the dispersity of the TCL/vinyl ester copolymers can be controlled via xanthate-mediated RAFT polymerization in the range of 5–20 kg mol⁻¹. Analysis of the copolymer structure shows a high level of TCL–TCL dyads, suggesting that the terminal copolymerization model does not accurately describe TCL copolymerization.

Due to their remarkable electronic features, recent years have witnessed the emergence of carbones L₂C, which consist in two donating L ligands coordinating a central carbon atom bearing two lone pairs. In this context, the phosphine/sulfoxide-supported carbone 4 exhibits a strong nucleophilic character, and here, we describe its ability to coordinate dichlorogermylene. Two original stable coordination complexes were obtained and fully characterized in solution and in the solid state by NMR spectroscopy and X-ray diffraction analysis, respectively. At 60 °C, in the presence of 4, the Ge(II)-complex 5 undergoes a slow isomerization that transforms the bis-ylide ligand into an yldiide.

Reaction of the pincer-type ligand L3 supported complex [L3PbBr][BArF24] (1) with Li[(C(=N2)TMS)] furnishes [L3Pb(C(=N2)TMS)][BArF24] (2). Diazo-compound 2 eliminates dinitrogen upon irradiation affording formal plumba-alkyne 3, which persists in cold fluoroarene solutions. Variable temperature UV/Vis and NMR spectroscopies in combination with quantum-chemical calculations identify 3 as a metal-substituted triplet carbene. In-crystallo irradiation of [L3Pb(C(=N2)TMS)(tol)][BArF24] (2∙tol) provides a snapshot of intermolecular C–H bond insertion with toluene (4).