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Keywords:

  • Photochemie;
  • Reduktive Eliminierung;
  • Stickstoff-Fixierung;
  • Zirconium

Abstract

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.