N2 hydrogenation from activated end-on bis(indenyl) zirconium dinitrogen complexes

Doris Pun, Christopher A. Bradley, Emil Lobkovsky, Ivan Keresztes, Paul J. Chirik

Research output: Contribution to journalArticle

44 Scopus citations

Abstract

Sodium amalgam reduction of the bis(indenyl)zirconium dihalide complexes, (η5-C9H5-1-iPr-3-Me)2ZrX2 (X = Cl, Br, I), yielded the corresponding end-on dinitrogen complexes, [(η5-C9H5-1-iPr-3-Me)2Zr(NaX)]22, η1, η1-N2), with inclusion of 1 equiv of salt per zirconocene. The solid state structures of the chloro and iodo congeners establish short Zr=N and elongated N-N bonds, consistent with modest to strong activation of the coordinated dinitrogen molecule. Exposure of the N2 compounds to 1 atm of dihydrogenresulted in rapid N-H bond formation to yield a hydrido zirconocene hydrazido compound concomitant with salt elimination. These studies establish a new structural type of zirconocene dinitrogen complex and demonstrate that side-on coordination of the N2 ligand in the ground state is not a prerequisite for dinitrogen hydrogenation.

Original languageEnglish (US)
Pages (from-to)14046-14047
Number of pages2
JournalJournal of the American Chemical Society
Volume130
Issue number43
DOIs
StatePublished - Oct 29 2008
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

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