Dinitrogen activation at iron and cobalt metallalumatranes

P. Alex Rudd, Nora Planas, Eckhard Bill, Laura Gagliardi, Connie C. Lu

Research output: Contribution to journalArticle

18 Scopus citations

Abstract

Anionic cobalt and iron metallalumatranes that bind dinitrogen in an end-on fashion were prepared and characterized by X-ray crystallography. Along with literature-known neutral cobalt and iron metallalumatranes, they form a quartet of low-valent coordination complexes for comparing dinitrogen activation and functionalization at cobalt versus iron centers. In the anionic metallalumatranes, the metal atoms are proposed to have subvalent oxidation states of -1. The electronic structure of the anionic iron alumatrane, which was probed by electron paramagnetic resonance spectroscopy, Mössbauer spectroscopy, and density functional theory, is most consistent with Fe(-1)→Al(+3). Functionalization of dinitrogen was achieved by reaction of the ferrate alumatrane with 1,2-bis(chlorodimethylsilyl)ethane and KC 8 (1 equiv.) to generate an iron(II) disilylhydrazido complex. The transformation of dinitrogen to disilylhydrazido(2-) is an overall fourelectron process.

Original languageEnglish (US)
Pages (from-to)3898-3906
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number22-23
DOIs
StatePublished - Oct 31 2013

Keywords

  • Aluminum
  • Metalloligands
  • Moessbauer spectroscopy
  • Nitrogen
  • Subvalent compounds

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