A general method for the preparation of zirconocene complexes of imines has been developed. The X-ray crystal structure of the (trimethylsilyl)benzaldimine complex 2b shows that these complexes should be viewed as metallaziridenes due to significant π-donation from the zirconium center to the π* orbitals of the coordinated imine. These complexes undergo a number of chemo-, region-, and diastereoselective coupling reactions with unsaturated organic compounds to cleanly form metallacyclic compounds. In situ generation of the complexes followed by coupling with alkynes and hydrolysis affords a general route to geometrically pure allylic amines.
