Themed collection Frontiers in Main Group Chemistry

The transition-metal-free syntheses of poly(aminoboranes) and poly(phosphinoboranes) are reviewed. These strategies focus on the generation of reactive aminoboranes or phosphinoboranes in situ, which then undergo polymerization.

The influence of substituents at the C vertices of oCbs on their reactivity with CAACs was investigated, providing new insight into the general mechanism of nucleophilic substitution at B centres.

Perfluoropinacolate complexes of Si and Ge possess Lewis superacid properties. They function as potent promoters in the reduction of highly stable PO, SO, and CO double bonds with PhSiH₃ and (EtO)₃SiH.

The reactions of the carborane-fused borirane (B₁₀H₁₀C₂)BN(SiMe₃)₂ (1) with isocyanides proceed, for the first time, with a clearly defined sequence of coordination and insertion steps.

Ambiphilic Sb–H bonds have been explored with both proton acceptors and hydride abstractors. Reactions with LiHMDS have also afforded a never-before-seen anionic triantimony chain as a lithium salt, and octameric antimony cluster.

Separation of lithium and sodium perchlorate through selective chelation of lithium perchlorate with the hexadentate ligand DETAN.

The high reactivity of a sterically accessible phosphonioacetylide was tamed via alkali metal coordination. The resulting complexes are precursors for introducing the rod-shaped, strongly electron-donating ligand into transition metal complexes.

CO₂ and EtNCO are inserted into the Ge–Si bonds of an NHC-bis(germylene) with nucleophilic Ge(II) lone-pairs and an electrophilic para-silylenearylene backbone. CAAC-induced fragmentation yields a germylene with a tethered CAAC-radical.