Dinitrogen silylation and cleavage with a hafnocene complex

Scott P. Semproni, Emil Lobkovsky, Paul J. Chirik

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Silylation of a hafnocene complex containing a strongly activated dinitrogen ligand, [(η5-C5H2-1,2,4-Me 3)2Hf]222, η2-N2), by addition of CySiH3 resulted in N-Si and Hf-H bond formation and a compound poised for subsequent N2 cleavage. Warming the silane addition product to 75 ° triggered N-N scission, for which the requisite electrons were provided by silyl migration. Dinitrogen cleavage coupled to N-C bond formation was also accomplished by carbonylation of the silylated product, yielding an unprecedented μ-formamidide ([NC(H)O]2-) ligand. Subsequent treatment with HCl yielded free formamide, demonstrating that an important organic molecule can be synthesized from N2, CO, an organosilane, and protons.

Original languageEnglish (US)
Pages (from-to)10406-10409
Number of pages4
JournalJournal of the American Chemical Society
Issue number27
StatePublished - Jul 13 2011

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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