TY - JOUR
T1 - Approaching a “Naked” Boryl Anion
T2 - Amide Metathesis as a Route to Calcium, Strontium, and Potassium Boryl Complexes
AU - Protchenko, Andrey V.
AU - Vasko, Petra
AU - Fuentes, M. Ángeles
AU - Hicks, Jamie
AU - Vidovic, Dragoslav
AU - Aldridge, Simon
N1 - Publisher Copyright:
© 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
PY - 2021/1/25
Y1 - 2021/1/25
N2 - Amide metathesis has been used to generate the first structurally characterized boryl complexes of calcium and strontium, {(Me3Si)2N}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)2Li- {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.
AB - Amide metathesis has been used to generate the first structurally characterized boryl complexes of calcium and strontium, {(Me3Si)2N}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)2Li- {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.
KW - atoms in molecules
KW - boron
KW - boryl
KW - s-block chemistry
KW - structural studies
UR - http://www.scopus.com/inward/record.url?scp=85096649577&partnerID=8YFLogxK
U2 - 10.1002/anie.202011839
DO - 10.1002/anie.202011839
M3 - Article
SN - 1433-7851
VL - 60
SP - 2064
EP - 2068
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 4
ER -