New example of a non-heme mononuclear iron(IV) oxo complex. Spectroscopic data and oxidation activity.
The green complex S=1 [(TPEN)FeO]2+ [TPEN=N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine] has been obtained by treating the [(TPEN)Fe]2+ precursor with meta-chloroperoxybenzoic acid (m-CPBA). This high-valent complex belongs to the emerging family of synthetic models of Fe(IV)=O intermediates invoked during the catalytic cycle of biological systems. This complex exhibits spectroscopic characteristics that are similar to those of other models reported recently with a similar amine/pyridine environment. Thanks to its relative stability, vibrational data in solution have been obtained by Fourier transform infrared. A comparison of the Fe=O and Fe=(18)O wavenumbers reveals that the Fe-oxo vibration is not a pure one. The ability of the green complex to oxidize small organic molecules has been studied. Mixtures of oxygenated products derived from two- or four-electron oxidations are obtained. The reactivity of this [FeO]2+ complex is then not straightforward, and different mechanisms may be involved.
Martinho
Marlène
M
Laboratoire de Chimie Inorganique, UMR 8613, Institut de Chimie Moléculaire et des Matériaux d'Orsay, Université Paris Sud, 91405 Orsay Cedex, France.
Banse
Frédéric
F
Bartoli
Jean-François
JF
Mattioli
Tony A
TA
Battioni
Pierrette
P
Horner
Olivier
O
Bourcier
Sophie
S
Girerd
Jean-Jacques
JJ
D005021:Ethylamines / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011725:Pyridines; D011743:Pyrimidines / Q000737:chemistry*; D012680:Sensitivity and Specificity; D012996:Solutions / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D014732:Vibration
D005021:Ethylamines; D008024:Ligands; C511824:N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine; D009942:Organometallic Compounds; D011725:Pyridines; D011743:Pyrimidines; D012996:Solutions; D007501:Iron; D010100:Oxygen