Photochemically induced reductive elimination as a route to a zirconocene complex with a strongly activated N2 ligand

Grant W. Margulieux, Scott P. Semproni, Paul J. Chirik

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

The zirconocene dinitrogen complex [{(η5-C 5Me4H)2Zr}22, η22-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-H activation or undergo comproportion to formally ZrIII complexes. When N2 is in excess arene displacement gives rise to strong dinitrogen activation. The zirconocene dinitrogen complex [{(η5-C5Me4H) 2Zr}222, η2-N2)] was synthesized by photochemical reductive elimination from the corresponding Zr bis(aryl) or aryl hydride complexes. Mechanistic studies support the intermediacy of zirconocene arene complexes that in the absence of sufficient N2 promote C-H activation. When N 2 is in excess arene displacement gives rise to strong dinitrogen activation.

Original languageEnglish (US)
Pages (from-to)9189-9192
Number of pages4
JournalAngewandte Chemie - International Edition
Volume53
Issue number35
DOIs
StatePublished - Aug 25 2014

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Keywords

  • nitrogen fixation
  • photochemistry
  • reductive elimination
  • zirconium

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