The
stepwise reduction of a doubly cyclic alkyl(amino)carbene (CAAC)-stabilized
2,3-bis(dibromoboryl)naphthalene enables the isolation of the corresponding
mono- and bis(boryl) radicals (one- and two-electron reduction), a
2π-aromatic 1,2-diborete (four-electron reduction), which shows
biradical character in the solid-state EPR spectrum, and its cyclic
bis(alkylidene)diboron dianion (six-electron reduction). The X-ray
crystallographic analysis of the diborete shows a highly strained
and twisted four-membered ring with a formal cis-diborene
motif featuring a very elongated B–B double bond. Calculations
based on DFT and multireference approaches reveal that the diborete
possesses an open-shell singlet biradicaloid ground state, which is
slightly energetically preferred to its EPR-active triplet-state congener.
The addition of CO to the diborete resulted in B–B bond splitting
and the formation of the corresponding closed-shell singlet, doubly
Lewis base-stabilized bis(borylene), whereas a twofold γ insertion
of phenyl azide generates a 1,3-bis(diazenyl)-1,3,2,4-diazadiboretidine.
Among a series of Lewis base-stabilised antiaromatic dibenzoberylloles (DBBes) the cyclic alkyl(amino)carbene (CAAC) analogue undergoes a complex but highly selective thermal decomposition, involving the breaking and making of four bonds...
We report the synthesis of a series of group 11 metal complexes with sterically demanding anionic nitrogen ligands based on the 1,2-azaborinine motif. The ligands, which share structural similarities with...
The alumole Cp3tAlC4Et4 (Cp3t = 1,2,4-tris(tert-butyl)cyclopentadienyl) is reported to be capable of transferring its butadiene moiety to aryl(dihalo)boranes to generate boroles through aluminum-boron exchange. The products feature a rare alkyl-substituted...
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