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Reactivity Enhancement of a Zerovalent Diboron Compound by Desymmetrization
Julian Böhnke1,2, Merle Arrowsmith1,2, Holger Braunschweig1,2
1Institut für Anorganische Chemie , Julius-Maximilians Universität Würzburg , Am Hubland, 97074 Würzburg , Germany.
Abstract:
The desymmetrization of the cyclic (alkyl)(amino)carbene-supported diboracumulene B2(cAACMe)2 (cAACMe = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) by monoadduct formation with IMeMe (1,3-dimethylimidazol-2-ylidene) yields the zerovalent sp-sp2 diboron compound B2(cAACMe)2(IMeMe), which provides a versatile platform for the synthesis of novel symmetrical and unsymmetrical zerovalent sp2-sp2 diboron compounds by adduct formation with IMeMe and CO, respectively. Furthermore, B2(cAACMe)2(IMeMe) displays enhanced reactivity compared to its symmetrical precursor, undergoing spontaneous intramolecular C-H activation and facile twofold hydrogenation, the latter resulting in B-B bond cleavage and the formation of the mixed-base parent borylene (cAACMe)(IMeMe)BH.
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