Nonheme oxoiron(IV) complexes of tris(2-pyridylmethyl)amine with cis-monoanionic ligands.
Treatment of [Fe(IV)(O)(TPA)(NCMe)](CF3SO3)2 [TPA, N,N,N-tris(2-pyridylmethyl)amine] with 3 equiv of NR4X (X = CF3CO2, Cl, or Br) in MeCN at -40 degrees C affords a series of metastable [Fe(IV)(O)(TPA)(X)]+ complexes. Some characteristic features of the S = 1 oxoiron(IV) unit are quite insensitive to the ligand substitution in the equatorial plane, namely, the Fe-O distances (1.65-1.66 A), the energy ( approximately 7114.5 eV) and intensity [25(2) units] of the 1s-to-3d transition in the X-ray absorption spectra, and the Mössbauer isomer shifts (0.01-0.06 mm.s(-1)) and quadrupole splittings (0.92-0.95 mm.s(-1)). The coordination of the anionic X ligand, however, is evidenced by red shifts of the characteristic near-IR ligand-field bands (720-800 nm) and spectroscopic observation of the bound anion by (19)F NMR for X = CF3CO2 and by EXAFS analysis for X = Cl (r(Fe-Cl) = 2.29 A) and Br (r(Fe-Br) = 2.43 A). Density functional theory calculations yield Mössbauer parameters and bond lengths in good agreement with the experimental data and produce excited-state energies that follow the trend observed in the ligand-field bands. Despite mitigating the high effective charge of the iron(IV) center, the substitution of the MeCN ligand with monoanionic ligands X- decreases the thermal stability of [Fe(IV)(O)(TPA)]2+ complexes. These anion-substituted complexes model the cis-X-Fe(IV)=O units proposed in the mechanisms of oxygen-activating nonheme iron enzymes.
Rohde
Jan-Uwe
JU
Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA.
Stubna
Audria
A
Bominaar
Emile L
EL
Münck
Eckard
E
Nam
Wonwoo
W
Que
Lawrence
L
D000838:Anions / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*
D000838:Anions; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; C431843:tris(2-pyridylmethyl)amine; C066317:ferryl iron; D007501:Iron; D010100:Oxygen