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

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 Pt^II−H intermediate engages in C(sp³)−H bond activation-induced dehydrogenation. [ABSTRACT FROM AUTHOR]