Isolation of Neutral, Mono‐, and Dicationic B(2)P(2) Rings by Diphosphorus Addition to a Boron−Boron Triple Bond

The NHC‐stabilised diboryne (B(2)(SIDep)(2); SIDep=1,3‐bis(2,6‐diethylphenyl)imidazolin‐2‐ylidene) undergoes a high‐yielding P−P bond activation with tetraethyldiphosphine at room temperature to form a B(2)P(2) heterocycle via a diphosphoryldiborene by 1,2‐diphosphination. The heterocycle can be oxidised to a radical cation and a dication, respectively, depending on the oxidant used and its counterion. Starting from the planar, neutral 1,3‐bis(alkylidene)‐1,3‐diborata‐2,4‐diphosphoniocyclobutane, each oxidation step leads to decreased B−B distances and loss of planarity by cationisation. X‐ray analyses in conjunction with DFT and CASSCF/NEVPT2 calculations reveal closed‐shell singlet, butterfly‐shaped structures for the NHC‐stabilised dicationic B(2)P(2) rings, with their diradicaloid, planar‐ring isomers lying close in energy.