Cobalt Boryl Complexes: Enabling and Exploiting Migratory Insertion in Base-Metal-Mediated Borylation.

Cobalt boryl complexes, which have only been sporadically reported, can be accessed systematically with remarkable (but controllable) variation in the nature of the M-B bond. Complexes incorporating a very strong trans σ-donor display unparalleled inertness, reflected in retention of the M-B bond even in the presence of extremely strong acid. By contrast, the use of the strong π-acceptor CO in the trans position, results in significant Co-B elongation and to labilization of the boryl ligand via unprecedented CO migratory insertion. Such chemistry provides a pathway for the generation of coordinative unsaturation, thereby enabling ligand substitution and/or substrate assimilation. Alkene functionalization by boryl transfer, a well-known reaction for noble metals such as Rh or Pt, can thus be effected by an 18-electron base-metal complex.

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