Metathesis Reactions of a NHC‐Stabilized Phosphaborene

The BP unsaturated unit is a very attractive functional group as it provides novel reactivity and unique physical properties. Nonetheless, applications remain limited so far due to the bulky nature of B/P‐protecting groups, required to prevent oligomerization. Herein, we report the synthesis and isolation of a N‐heterocyclic carbene (NHC)‐stabilized phosphaborene, bearing a trimethylsilyl (TMS) functionality at the P‐terminal, as a room‐temperature‐stable crystalline solid accessible via facile NHC‐induced trimethylsilyl chloride (TMSCl) elimination from its phosphinoborane precursor. This phosphaborene compound, bearing a genuine B=P bond, exhibits a remarkable ability for undergoing P‐centre metathesis reactions, which allows the isolation of a series of unprecedented phosphaborenes. X‐ray crystallographic analysis, UV/Vis spectroscopy, and DFT calculations provide insights into the B=P bonding situation.