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

Friedrich A, Eyselein J, Langer J, Färber C, Harder S (2021)

Publication Type: Journal article

Publication year: 2021

Journal

DOI: 10.1002/anie.202103250

Abstract

Low-valent ((BDI)-B-Me)Al and ((BDI)-B-Me)Ga and highly Lewis acidic cations in [((BDI)-B-tBu)M+.C6H6][(B(C6F5)(4)(-)] (M=Mg or Zn, (BDI)-B-Me=HC[C(Me)N-DIPP](2), (BDI)-B-tBu=HC[C(tBu)N-DIPP](2), DIPP=2,6-diisopropylphenyl) react to heterobimetallic cations [((BDI)-B-tBu)Mg-Al((BDI)-B-Me)(+)], [((BDI)-B-tBu)Mg-Ga((BDI)-B-Me)(+)] and [((BDI)-B-tBu)Zn-Ga((BDI)-B-Me)(+)]. These cations feature long Mg-Al (or Ga) bonds while the Zn-Ga bond is short. The [((BDI)-B-tBu)Zn-Al((BDI)-B-Me)(+)] 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 Al-I(or Ga-I)-> Mg2+ donor bonds. Failure to isolate the Zn-Al combination originates from cleavage of the C-F bond in the solvent fluorobenzene to give ((BDI)-B-tBu)ZnPh and ((BDI)-B-Me)AlF+ which is extremely Lewis acidic and was not observed, but ((BDI)-B-Me)Al(F)-(mu-F)-(F)Al((BDI)-B-Me)(+) was verified by X-ray diffraction. DFT calculations show that the remarkably facile C-F bond cleavage follows a dearomatization/rearomatization route.

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How to cite

APA:

Friedrich, A., Eyselein, J., Langer, J., Färber, C., & Harder, S. (2021). Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C-F Bond Cleavage. Angewandte Chemie International Edition. https://doi.org/10.1002/anie.202103250

MLA:

Friedrich, Alexander, et al. "Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C-F Bond Cleavage." Angewandte Chemie International Edition (2021).

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