Redox-Induced N2 Hapticity Switching in Zirconocene Dinitrogen Complexes


  • We thank the Director of the Office of Basic Energy Science, Chemical Sciences Division, U.S. Department of Energy (DE-FG-02-05ER15659) and the ACS Frasch Foundation for financial support. S.P.S. thanks the Natural Sciences and Engineering Research Council of Canada for a predoctoral fellowship and C.M. also acknowledges the Alexander von Humboldt Foundation for a Feodor Lynen postdoctoral fellowship.


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N2 shuffle: One-electron reduction of the ansa-zirconocene complex with a side-on dinitrogen ligand furnished the corresponding anion in which the hapticity of the N2 ligand changed to end-on. Oxidation of the anion regenerates the neutral complex with concomitant change in N2 hapticity. The zirconocene complexes with unusual (N2)3−/(N2) ligands have been fully characterized. Ad=adamantyl.