Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C-F Bond Cleavage.

Low-valent (Me BDI)Al and (Me BDI)Ga and highly Lewis acidic cations in [(tBu BDI)M+ ⋅C6 H6 ][(B(C6 F5 )4 - ] (M=Mg or Zn, Me BDI=HC[C(Me)N-DIPP]2 , tBu BDI=HC[C(tBu)N-DIPP]2 , DIPP=2,6-diisopropylphenyl) react to heterobimetallic cations [(tBu BDI)Mg-Al(Me BDI)+ ], [(tBu BDI)Mg-Ga(Me BDI)+ ] and [(tBu BDI)Zn-Ga(Me BDI)+ ]. These cations feature long Mg-Al (or Ga) bonds while the Zn-Ga bond is short. The [(tBu BDI)Zn-Al(Me BDI)+ ] cation was not formed. Combined AIM and charge calculations suggest that the metal-metal bonds to Zn are considerably more covalent, whereas those to Mg should be described as weak AlI (or GaI )→Mg2+ donor bonds. Failure to isolate the Zn-Al combination originates from cleavage of the C-F bond in the solvent fluorobenzene to give (tBu BDI)ZnPh and (Me BDI)AlF+ which is extremely Lewis acidic and was not observed, but (Me BDI)Al(F)-(μ-F)-(F)Al(Me BDI)+ was verified by X-ray diffraction. DFT calculations show that the remarkably facile C-F bond cleavage follows a dearomatization/rearomatization route.