Isolation and Characterization of Crystalline, Neutral Diborane(4) Radicals

Diaryldihalodiboranes(4) were reacted with bis(amidinato)‐ and bis(guanidinato)silylenes to generate the first neutral diborane‐centered radicals. These formally non‐aromatic 5π electron systems are stable in the solid state as well as in solution and were characterized by solid‐state structure determination, high‐resolution mass spectrometry, and EPR spectroscopy. The reactivity of one of these radicals with the oxidant 1,4‐benzoquinone led to ring‐opening and B−O bond formation. Solid as a rock: Diaryldihalodiboranes(4) were reacted with bis(amidinato)‐ and bis(guanidinato)silylenes to generate the first neutral diborane‐centered radicals. These formally non‐aromatic 5π electron systems are stable in the solid state as well as in solution.