Evidence for Borylene Carbonyl (LHB═C═O) and Base-Stabilized (LHB═O) and Base-Free Oxoborane (RB≡O) Intermediates in the Reactions of Diborenes with CO<sub>2</sub>
Andreas Stoy, Marcel Härterich, Rian D. Dewhurst, J. Óscar C. Jiménez‐Halla, Peter Endres, Maximilian Eyßelein, Thomas Kupfer, Andrea Deißenberger, Torsten Thiess, Holger Braunschweig
Abstract
, initially providing dibora-β-lactones. These lactones convert over time to their 2,4-diboraoxetan-3-one isomers through a presumed dissociative pathway and hypovalent boron species borylene carbonyls (LHB═C═O) and base-stabilized oxoboranes (LHB═O). Repeating these reactions with doubly cyclic(alkyl)(amino)carbene-stabilized diborenes allowed the isolation of a borylene carbonyl intermediate, whereas a base-stabilized oxoborane could be inferred by the isolation of a boroxine from the reaction mixture. These results, supported by calculations, confirm the presumed mechanism of the diboralactone-to-diboraoxetanone isomerization while also establishing a surprising level of stability for three unknown or very rare hypovalent boron species: base-stabilized derivatives of the parent borylene carbonyl (LHB═C═O) and parent oxoborane (LHB═O) as well as base-free oxoboranes (RB≡O).