A low-spin d5 iron imide: nitrene capture by low-coordinate iron(I) provides the 4-coordinate Fe(III) complex [PhB(CH2PPh2)3]Fe=N-p-tolyl

J Am Chem Soc. 2003 Jan 15;125(2):322-3. doi: 10.1021/ja028448i.

Abstract

Entry into "[PhBP3]Fe" chemistry affords a rare, pseudotetrahedral iron(I) complex, [PhBP3]Fe(PPh3), with an S = 3/2 ground state. This precursor undergoes rapid oxidation by aryl azide to produce the d5 imide [PhBP3]FeNAr (Ar = p-tolyl). The Fe(III) imide is significant in that it is low-spin and represents the first mononuclear imide of iron. Doublet [PhBP3]FeNAr reacts rapidly and quantitatively with CO at room temperature to release isocyanate and [PhBP3]Fe(CO)2. The [PhBP3]Fe(CO)2 byproduct is also a precursor to [PhBP3]FeNAr upon addition of aryl azide.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Biomimetic Materials / chemistry
  • Electron Spin Resonance Spectroscopy
  • Hydrogenase / chemistry
  • Imides / chemistry*
  • Iron Compounds / chemistry*
  • Nitrogenase / chemistry
  • Organometallic Compounds / chemistry*

Substances

  • (tris(diphenylphosphinomethyl)phenylborate)(p-tolylnitrido)iron(I)
  • Imides
  • Iron Compounds
  • Organometallic Compounds
  • Hydrogenase
  • Nitrogenase