Selective transformations of organic compounds by imidozirconocene complexes

Imidozirconocene complexes (Cp(2)Zr=NR(THF)) possess a rich reaction chemistry, in contrast to many imido complexes of later transition metals. The synthesis and structural characteristics of these compounds are briefly described, along with a qualitative molecular orbital description of the metallocene-imido interaction. Imidozirconocene complexes react at the Zr=N linkage with a variety of X-H bonds, and undergo overall [2 + 2] cycloaddition reactions with a wide range of unsaturated organic and organometallic compounds. Results of studies detailing the scope and mechanism of these reactions are presented herein, along with applications to catalytic hydroamination, imine metathesis, and asymmetric transformations.