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Approaching a "Naked" Boryl Anion: Amide Metathesis as a Route to Calcium, Strontium, and Potassium Boryl Complexes.


ABSTRACT: Amide metathesis has been used to generate the first structurally characterized boryl complexes of calcium and strontium, {(Me3 Si)2 N}M{B(NDippCH)2 }(thf)n (M=Ca, n=2; M=Sr, n=3), through the reactions of the corresponding bis(amides), M{N(SiMe3 )2 }2 (thf)2 , with (thf)2 Li- {B(NDippCH)2 }. Most notably, this approach can also be applied to the analogous potassium amide K{N(SiMe3 )2 }, leading to the formation of the solvent-free borylpotassium dimer [K{B(NDippCH)2 }]2 , which is stable in the solid state at room temperature for extended periods (48?h). A dimeric structure has been determined crystallographically in which the K+ cations interact weakly with both the ipso-carbons of the flanking Dipp groups and the boron centres of the diazaborolyl heterocycles, with K???B distances of >3.1?Å. These structural features, together with atoms in molecules (QTAIM) calculations imply that the boron-containing fragment closely approaches a limiting description as a "free" boryl anion in the condensed phase.

SUBMITTER: Protchenko AV 

PROVIDER: S-EPMC7894291 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

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Approaching a "Naked" Boryl Anion: Amide Metathesis as a Route to Calcium, Strontium, and Potassium Boryl Complexes.

Protchenko Andrey V AV   Vasko Petra P   Fuentes M Ángeles MÁ   Hicks Jamie J   Vidovic Dragoslav D   Aldridge Simon S  

Angewandte Chemie (International ed. in English) 20201123 4


Amide metathesis has been used to generate the first structurally characterized boryl complexes of calcium and strontium, {(Me<sub>3</sub> Si)<sub>2</sub> N}M{B(NDippCH)<sub>2</sub> }(thf)<sub>n</sub> (M=Ca, n=2; M=Sr, n=3), through the reactions of the corresponding bis(amides), M{N(SiMe<sub>3</sub> )<sub>2</sub> }<sub>2</sub> (thf)<sub>2</sub> , with (thf)<sub>2</sub> Li- {B(NDippCH)<sub>2</sub> }. Most notably, this approach can also be applied to the analogous potassium amide K{N(SiMe<sub>3<  ...[more]

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