Regioselective C–H Activation Preceded by Csp2–Csp3 Reductive Elimination from Cyclometalated Platinum(IV) Complexes

Abstract

Reductive elimination reactions of the cyclometalated platinum(IV) compounds [PtMe2Cl{C6H4CH═NCH2(4-ClC6H4)}L] and [PtMe2Br{C6H4CH═NCH2(C6H5)}L] (L = SMe2, PPh3) to form Csp3–Csp2 bonds, followed by either exclusive Csp2–H bond activation (L = SMe2) or competition between Csp2–H and Csp3–H bond activation (L = PPh3), are reported. Isomerization to give endo products instead of the expected exo complex was observed for the ligand C6H4CH═NCH2(2-BrC6H5), and formation of an endo six-membered platinacycle occurs for the ligand 2,4,6-Me3C6H2CH═NCH2(2-BrC6H4).