Cargando…

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(+)⋅C(6)H(6)][(B(C(6)F(5))(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–G...

Descripción completa

Detalles Bibliográficos
Autores principales: Friedrich, Alexander, Eyselein, Jonathan, Langer, Jens, Färber, Christian, Harder, Sjoerd
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8361950/
https://www.ncbi.nlm.nih.gov/pubmed/33979476
http://dx.doi.org/10.1002/anie.202103250
_version_ 1783738052276912128
author Friedrich, Alexander
Eyselein, Jonathan
Langer, Jens
Färber, Christian
Harder, Sjoerd
author_facet Friedrich, Alexander
Eyselein, Jonathan
Langer, Jens
Färber, Christian
Harder, Sjoerd
author_sort Friedrich, Alexander
collection PubMed
description Low‐valent ((Me)BDI)Al and ((Me)BDI)Ga and highly Lewis acidic cations in [((tBu)BDI)M(+)⋅C(6)H(6)][(B(C(6)F(5))(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 Al(I)(or Ga(I))→Mg(2+) 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.
format Online
Article
Text
id pubmed-8361950
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher John Wiley and Sons Inc.
record_format MEDLINE/PubMed
spelling pubmed-83619502021-08-17 Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage Friedrich, Alexander Eyselein, Jonathan Langer, Jens Färber, Christian Harder, Sjoerd Angew Chem Int Ed Engl Research Articles Low‐valent ((Me)BDI)Al and ((Me)BDI)Ga and highly Lewis acidic cations in [((tBu)BDI)M(+)⋅C(6)H(6)][(B(C(6)F(5))(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 Al(I)(or Ga(I))→Mg(2+) 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. John Wiley and Sons Inc. 2021-06-19 2021-07-19 /pmc/articles/PMC8361950/ /pubmed/33979476 http://dx.doi.org/10.1002/anie.202103250 Text en © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Articles
Friedrich, Alexander
Eyselein, Jonathan
Langer, Jens
Färber, Christian
Harder, Sjoerd
Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage
title Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage
title_full Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage
title_fullStr Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage
title_full_unstemmed Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage
title_short Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage
title_sort cationic heterobimetallic mg(zn)/al(ga) combinations for cooperative c–f bond cleavage
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8361950/
https://www.ncbi.nlm.nih.gov/pubmed/33979476
http://dx.doi.org/10.1002/anie.202103250
work_keys_str_mv AT friedrichalexander cationicheterobimetallicmgznalgacombinationsforcooperativecfbondcleavage
AT eyseleinjonathan cationicheterobimetallicmgznalgacombinationsforcooperativecfbondcleavage
AT langerjens cationicheterobimetallicmgznalgacombinationsforcooperativecfbondcleavage
AT farberchristian cationicheterobimetallicmgznalgacombinationsforcooperativecfbondcleavage
AT hardersjoerd cationicheterobimetallicmgznalgacombinationsforcooperativecfbondcleavage