Dehydrogenative B−H/C(sp3)−H Benzylic Borylation within the Coordination Sphere of Platinum(II)

Abstract The first examples of stoichiometric dehydrogenative B−H/C(sp3)−H benzylic borylation reactions, which are of relevance to catalytic methylarene (di)borylation, are reported. These unusual transformations involving a (κ2‐P,N)Pt(η3‐benzyl) complex, and either pinacolborane or catecholborane, proceed cleanly at room temperature. Density functional calculations suggest that borylation occurs via successive σ‐bond metathesis steps, whereby a PtII−H intermediate engages in C(sp3)−H bond activation‐induced dehydrogenation.