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

Amide metathesis has been used to generate the first structurally characterized boryl complexes of calcium and strontium, {(Me(3)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(SiMe(3))(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(SiMe(3))(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.