Diboriranide σ-Complexes of d- and p-Block Metals

Diboriranides are the smallest conceivable monoanionic aromatic cycles, yet only limited examples have been reported and their reactivity and complexation behavior remain completely unexplored. We report a straightforward synthesis of the first peraryl diboriranide c-(DurB)2CPh as its lithium salt in three steps via the corresponding non-classical diborirane from a readily available 1,2-dichlorodiborane(4) (Dur= 2,3,5,6-tetramethylphenyl). With the preparation and complete characterization of representative complexes with tin, copper, gold and zinc, we demonstrate the strong preference of the diboriranide for σ-type coordination modes towards main group and transition metal centers under unperturbed retention of the threemembered B2C-ring’s 2e π-system