Cationic Gold(III) Alkyl Complexes: Generation, Trapping, and Insertion of Norbornene

Migratory insertion of alkenes into gold–carbon bonds, a fundamental yet unprecedented organometallic transformation, has been investigated from a discrete (P,C) cyclometalated gold(III) dimethyl complex. Methide ion by B(C6F5)3 is shown to generate a highly reactive cationic AuIII complex that evolves spontaneously by C6F5 transfer from boron. In the presence of norbornene, migratory insertion into the AuC bond proceeds readily. The resulting norbornyl complex is efficiently trapped with pyridines or chloride to give stable four‐coordinate adducts. Migratory insertion of alkenes into gold–carbon bonds, a key yet unprecedented organometallic reaction, is observed. Methide ion from a (P,C) cyclometalated gold(III) dimethyl complex with B(C6F5)3 generates a highly reactive cationic AuIII complex. In the presence of norbornene, migratory insertion into the AuC bond proceeds at low temperature. The resulting norbornyl complex was trapped with pyridines and chloride.