Hydroalkylation of Aryl Alkenes with Organohalides Catalyzed by Molybdenum Oxido Based Lewis Pairs

Three molybdenum(VI) dioxido complexes [MoO(2)(L)(2)] bearing Schiff base ligands were reacted with B(C(6)F(5))(3) to afford the corresponding adducts [MoO{OB(C(6)F(5))(3)}(L)(2)], which were fully characterized. They exhibit Frustrated Lewis‐Pairs reactivity when reacting with silanes. Especially, the [MoO{OB(C(6)F(5))(3)}(L)(2)] complex with L=2,4‐dimethyl‐6‐((phenylimino)methyl)phenol proved to be active as catalyst for the hydroalkylation of aryl alkenes with organohalides and for the Atom‐Transfer Radical Addition (ATRA) of organohalides to aliphatic alkenes. A series of gem‐dichloride and gem‐dibromide compounds with potential for further derivatization were synthesized from simple alkenes and organohalides, like chloroform or bromoform, using low catalyst loading. [Image: see text]