The importance of cyclopentadienyl substituent effects in group 4 metallocene dinitrogen chemistry

This article highlights some of our recent efforts and presents new data on the importance of cyclopentadienyl substituent effects on group 4 metallocene dinitrogen chemistry. Reactions such as the coordination of N₂ to an isolated titanium sandwich complex, alkali-metal reductions of zirconocene dihalide complexes, alkane reductive elimination reactions, and the hydrogenation of zirconium dinitrogen complexes are all extremely sensitive to the groups present on the cyclopentadienyl rings. These results are promising for the future of N₂ fixation, as the reactivity of a specific metallocene can be dramatically altered by subtle manipulations in ligand substituents.