Abstract

Bending the planar trigonal boron atom of triphenylborane by connecting its aryl rings with carbon or phosphorus linkers gave access to a series of 9‐boratriptycene derivatives with unprecedented structures and reactivities. NMR and X‐ray diffraction investigations of the Lewis adducts of these non‐planar boron Lewis acids with weak Lewis bases (OPEt 3 , CH 3 CN, EtOAc, Cl – , Br – , I – ) revealed particularly strong covalent bond formation. The first Lewis adduct of a trivalent boron compounds with the Tf 2 N – anion is reported, illustrating the unrivaled Lewis acidity of these pyramidalized boron Lewis acids. Experimental and quantum‐chemical investigations showed that increasing the pyramidalization of the boron atom and using a cationic phosphonium linker resulted in an exceptional enhancement of Lewis acidity, pushing forward the boundaries of the Lewis acidity scale of trivalent boron Lewis acids. Introduction of a phosphorus and a boron atom at each edge of a triptycene framework, allowed to access new bifunctional Lewis acid‐base 9‐phospha‐10‐boratriptycenes featuring promising reactivity for the activation of carbon‐halogen bonds.
Original languageEnglish
Pages (from-to)16889-16893
Number of pages5
JournalAngewandte Chemie International Edition
Volume58
Issue number47
DOIs
Publication statusPublished - 18 Nov 2019

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Boron Compounds
Boron compounds
Boron
Acidity
Lewis Acids
Atoms
Phosphorus
Acids
Lewis Bases
Covalent bonds
Anions
Negative ions
Carbon
Diffraction
Chemical activation
Nuclear magnetic resonance
Derivatives

Keywords

  • boron
  • Lewis acids
  • Lewis superacid
  • non-planar
  • triarylboranes

Cite this

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title = "Pushing the Lewis Acidity Boundaries of Boron Compounds With Non‐Planar Triarylboranes Derived from Triptycenes",
abstract = "Bending the planar trigonal boron atom of triphenylborane by connecting its aryl rings with carbon or phosphorus linkers gave access to a series of 9‐boratriptycene derivatives with unprecedented structures and reactivities. NMR and X‐ray diffraction investigations of the Lewis adducts of these non‐planar boron Lewis acids with weak Lewis bases (OPEt 3 , CH 3 CN, EtOAc, Cl – , Br – , I – ) revealed particularly strong covalent bond formation. The first Lewis adduct of a trivalent boron compounds with the Tf 2 N – anion is reported, illustrating the unrivaled Lewis acidity of these pyramidalized boron Lewis acids. Experimental and quantum‐chemical investigations showed that increasing the pyramidalization of the boron atom and using a cationic phosphonium linker resulted in an exceptional enhancement of Lewis acidity, pushing forward the boundaries of the Lewis acidity scale of trivalent boron Lewis acids. Introduction of a phosphorus and a boron atom at each edge of a triptycene framework, allowed to access new bifunctional Lewis acid‐base 9‐phospha‐10‐boratriptycenes featuring promising reactivity for the activation of carbon‐halogen bonds.",
keywords = "boron, Lewis acids, Lewis superacid, non-planar, triarylboranes",
author = "{Ben Saida}, Ali and Aur{\'e}lien Chardon and Arnaud Osi and Nikolay Tumanov and Johan Wouters and Adjieufack, {Abel Idrice} and Beno{\^i}t Champagne and Guillaume Berionni",
year = "2019",
month = "11",
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TY - JOUR

T1 - Pushing the Lewis Acidity Boundaries of Boron Compounds With Non‐Planar Triarylboranes Derived from Triptycenes

AU - Ben Saida, Ali

AU - Chardon, Aurélien

AU - Osi, Arnaud

AU - Tumanov, Nikolay

AU - Wouters, Johan

AU - Adjieufack, Abel Idrice

AU - Champagne, Benoît

AU - Berionni, Guillaume

PY - 2019/11/18

Y1 - 2019/11/18

N2 - Bending the planar trigonal boron atom of triphenylborane by connecting its aryl rings with carbon or phosphorus linkers gave access to a series of 9‐boratriptycene derivatives with unprecedented structures and reactivities. NMR and X‐ray diffraction investigations of the Lewis adducts of these non‐planar boron Lewis acids with weak Lewis bases (OPEt 3 , CH 3 CN, EtOAc, Cl – , Br – , I – ) revealed particularly strong covalent bond formation. The first Lewis adduct of a trivalent boron compounds with the Tf 2 N – anion is reported, illustrating the unrivaled Lewis acidity of these pyramidalized boron Lewis acids. Experimental and quantum‐chemical investigations showed that increasing the pyramidalization of the boron atom and using a cationic phosphonium linker resulted in an exceptional enhancement of Lewis acidity, pushing forward the boundaries of the Lewis acidity scale of trivalent boron Lewis acids. Introduction of a phosphorus and a boron atom at each edge of a triptycene framework, allowed to access new bifunctional Lewis acid‐base 9‐phospha‐10‐boratriptycenes featuring promising reactivity for the activation of carbon‐halogen bonds.

AB - Bending the planar trigonal boron atom of triphenylborane by connecting its aryl rings with carbon or phosphorus linkers gave access to a series of 9‐boratriptycene derivatives with unprecedented structures and reactivities. NMR and X‐ray diffraction investigations of the Lewis adducts of these non‐planar boron Lewis acids with weak Lewis bases (OPEt 3 , CH 3 CN, EtOAc, Cl – , Br – , I – ) revealed particularly strong covalent bond formation. The first Lewis adduct of a trivalent boron compounds with the Tf 2 N – anion is reported, illustrating the unrivaled Lewis acidity of these pyramidalized boron Lewis acids. Experimental and quantum‐chemical investigations showed that increasing the pyramidalization of the boron atom and using a cationic phosphonium linker resulted in an exceptional enhancement of Lewis acidity, pushing forward the boundaries of the Lewis acidity scale of trivalent boron Lewis acids. Introduction of a phosphorus and a boron atom at each edge of a triptycene framework, allowed to access new bifunctional Lewis acid‐base 9‐phospha‐10‐boratriptycenes featuring promising reactivity for the activation of carbon‐halogen bonds.

KW - boron

KW - Lewis acids

KW - Lewis superacid

KW - non-planar

KW - triarylboranes

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