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.
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.
Brown
Steven D
SD
Division of Chemistry and Chemical Engineering, Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, USA.
Betley
Theodore A
TA
Peters
Jonas C
JC
D040761:Biomimetic Materials / Q000737:chemistry; D004578:Electron Spin Resonance Spectroscopy; D006864:Hydrogenase / Q000737:chemistry; D007094:Imides / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry*; D009591:Nitrogenase / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry*
C472024:(tris(diphenylphosphinomethyl)phenylborate)(p-tolylnitrido)iron(I); D007094:Imides; D058085:Iron Compounds; D009942:Organometallic Compounds; D006864:Hydrogenase; D009591:Nitrogenase