N-C bond formation promoted by a hafnocene dinitrogen complex: Comparison of zirconium and hafnium congeners

Wesley H. Bernskoetter, Andrea V. Olmos, Jaime A. Pool, Emil Lobkovsky, Paul J. Chirik

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Abstract

Nitrogen-carbon bond formation from coordinated dinitrogen has been observed upon addition of 2 equiv of PhNCO to the hafnocene dinitrogen complex, [(η5-C5Me4H)2Hf]2222-N2). The resulting product most likely arises from initial N=C cycloaddition of the first equivalent of heterocumulene, followed by carbonyl insertion of a second equivalent into the newly formed hafnium-nitrogen bond. The resulting product has considerable hafnium imido character, as evidenced by the metrical parameters determined from the solid-state structure as well as reactivity studies, whereby PhNCO, p-tolyl isocyanate, and t-BuCCH each undergo cycloaddition with the hafnium-nitrogen bond. The origin of the nitrogen-carbon-forming chemistry is likely derived from the reluctance of the hafnocene dinitrogen complex to undergo ligand-induced N2 isomerization, as was observed with the zirconium congener.

Original languageEnglish (US)
Pages (from-to)10696-10697
Number of pages2
JournalJournal of the American Chemical Society
Volume128
Issue number33
DOIs
StatePublished - Aug 23 2006
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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