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

The first examples of stoichiometric dehydrogenative B-H/C(sp(3))-H benzylic borylation reactions, which are of relevance to catalytic methylarene (di)borylation, are reported. These unusual transformations involving a (kappa(2)-P,N)Pt(eta(3)-benzyl) complex, and either pinacolborane or catecholborane, proceed cleanly at room temperature. Density functional calculations suggest that borylation occurs via successive sigma-bond metathesis steps, whereby a Pt-II-H intermediate engages in C(sp(3))-H bond activation-induced dehydrogenation.