Carboxylation of an ansa-zirconocene dinitrogen complex: Regiospecific hydrazine synthesis from N2 and CO2

Donald J. Knobloch, Hannah E. Toomey, Paul J. Chirik

Research output: Contribution to journalArticle

41 Scopus citations

Abstract

Addition of 2 equiv of carbon dioxide to the ansa-zirconocene dinitrogen complex resulted in selective insertion into each zirconium nitrogen bond, forming a C2 symmetric dicarboxylated diazenido compound. Treatment with excess Me3SiI furnished the ansa-zirconocene diiodide along with the N,N-dicarboxylated silylated hydrazine. New nitrogen-carbon bonds were also assembled by addition of methyl triflate. Tri- and tetrasubstituted hydrazines could be formed by treatment with water and Me3SiI, respectively. The regiochemistry of the N2 carboxylation is controlled by the ansa-cyclopentadienyl ligand where the sterically demanding tert-butyl substituents and the C2 symmetry of the dimer dictates the stereochemistry of CO2 insertion. These results demonstrate the ability of zirconium dinitrogen compounds to participate in heterocumulene insertion chemistry.

Original languageEnglish (US)
Pages (from-to)4248-4249
Number of pages2
JournalJournal of the American Chemical Society
Volume130
Issue number13
DOIs
StatePublished - Apr 2 2008
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

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