Photochemically Induced Reductive Elimination as a Route to a Zirconocene Complex with a Strongly Activated N2 Ligand


  • We thank the Department of Energy, Basic Energy and Sciences (DE-SC0006498) for financial support. Dr. Carsten Milsmann is also acknowledged for assistance with TD-DFT.


The zirconocene dinitrogen complex [{(η5-C5Me4H)2Zr}2222-N2)] was synthesized by photochemical reductive elimination from the corresponding zirconium bis(aryl) or aryl hydride complexes, providing a high-yielding, alkali metal-free route to strongly activated early-metal N2 complexes. Mechanistic studies support the intermediacy of zirconocene arene complexes that in the absence of sufficient dinitrogen promote C[BOND]H activation or undergo comproportion to formally ZrIII complexes. When N2 is in excess arene displacement gives rise to strong dinitrogen activation.