Nonheme Oxoiron(IV) Complexed of Tris(2-pyridylmethyl)amine with cis-Monoanionic Ligands

doi:https://doi.org/10.1021/ic060740u

Title: Nonheme Oxoiron(IV) Complexed of Tris(2-pyridylmethyl)amine with cis-Monoanionic Ligands

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Abstract

Treatment of [Fe{sup IV}(O)(TPA)(NCMe)](CF{sub 3}SO{sub 3}){sub 2} [TPA, N,N,N-tris(2-pyridylmethyl)amine] with 3 equiv of NR{sub 4}X (X = CF{sub 3}CO{sub 2}, Cl, or Br) in MeCN at -40 C affords a series of metastable [Fe{sup IV}(O)(TPA)(X)]{sup +} 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 Angstroms), the energy ({approx}7114.5 eV) and intensity [25(2) units] of the 1s-to-3d transition in the X-ray absorption spectra, and the M{umlt o}ssbauer isomer shifts (0.01-0.06 mm{center_dot}s{sup -1}) and quadrupole splittings (0.92-0.95 mm{center_dot}s{sup -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 19F NMR for X = CF{sub 3}CO{sub 2} and by EXAFS analysis for X = Cl (r{sub Fe-Cl} = 2.29 Angstroms) and Br (r{sub Fe-Br} = 2.43 Angstroms). Density functional theory calculations yield M{umlt o}ssbauer 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 ligandmore »« less

Authors:: Rohde, J; Stubna, A; Bominaar, E; Munck, E; Nam, W

Publication Date:: 2006-01-01

Research Org.:: Brookhaven National Laboratory (BNL) National Synchrotron Light Source

Sponsoring Org.:: Doe - Office Of Science

OSTI Identifier:: 914098

Report Number(s):: BNL-78666-2007-JA
Journal ID: ISSN 0020-1669; INOCAJ; TRN: US0801543

DOE Contract Number:: DE-AC02-98CH10886

Resource Type:: Journal Article

Journal Name:: Inorg. Chem.

Additional Journal Information:: Journal Volume: 45; Journal Issue: 16; Journal ID: ISSN 0020-1669

Country of Publication:: United States

Language:: English

Subject:: 43 PARTICLE ACCELERATORS; ABSORPTION SPECTRA; ANIONS; BOND LENGTHS; EFFECTIVE CHARGE; ENZYMES; FUNCTIONALS; IRON; ISOMER SHIFT; QUADRUPOLES; STABILITY; LIGANDS; NSLS; national synchrotron light source

Citation Formats


                    Rohde, J, Stubna, A, Bominaar, E, Munck, E, Nam, W, and Que, Jr., L. Nonheme Oxoiron(IV) Complexed of Tris(2-pyridylmethyl)amine with cis-Monoanionic Ligands.  United States: N. p., 2006. 
        Web.  doi:10.1021/ic060740u.

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                    Rohde, J, Stubna, A, Bominaar, E, Munck, E, Nam, W, & Que, Jr., L. Nonheme Oxoiron(IV) Complexed of Tris(2-pyridylmethyl)amine with cis-Monoanionic Ligands.  United States.  https://doi.org/10.1021/ic060740u

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                    Rohde, J, Stubna, A, Bominaar, E, Munck, E, Nam, W, and Que, Jr., L. Sun .  
        "Nonheme Oxoiron(IV) Complexed of Tris(2-pyridylmethyl)amine with cis-Monoanionic Ligands".  United States.  https://doi.org/10.1021/ic060740u.

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@article{osti_914098,

  title        = {Nonheme Oxoiron(IV) Complexed of Tris(2-pyridylmethyl)amine with cis-Monoanionic Ligands},

  author       = {Rohde, J and Stubna, A and Bominaar, E and Munck, E and Nam, W and Que, Jr., L.},

  abstractNote = {Treatment of [Fe{sup IV}(O)(TPA)(NCMe)](CF{sub 3}SO{sub 3}){sub 2} [TPA, N,N,N-tris(2-pyridylmethyl)amine] with 3 equiv of NR{sub 4}X (X = CF{sub 3}CO{sub 2}, Cl, or Br) in MeCN at -40 C affords a series of metastable [Fe{sup IV}(O)(TPA)(X)]{sup +} 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 Angstroms), the energy ({approx}7114.5 eV) and intensity [25(2) units] of the 1s-to-3d transition in the X-ray absorption spectra, and the M{umlt o}ssbauer isomer shifts (0.01-0.06 mm{center_dot}s{sup -1}) and quadrupole splittings (0.92-0.95 mm{center_dot}s{sup -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 19F NMR for X = CF{sub 3}CO{sub 2} and by EXAFS analysis for X = Cl (r{sub Fe-Cl} = 2.29 Angstroms) and Br (r{sub Fe-Br} = 2.43 Angstroms). Density functional theory calculations yield M{umlt o}ssbauer 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{sup -} decreases the thermal stability of [Fe{sup IV}(O)(TPA)]{sup 2+} complexes. These anion-substituted complexes model the cis-X-Fe{sup IV}=O units proposed in the mechanisms of oxygen-activating nonheme iron enzymes.},

  doi          = {10.1021/ic060740u},

  url          = {https://www.osti.gov/biblio/914098},
  journal      = {Inorg. Chem.},

  issn         = {0020-1669},

  number       = 16,

  volume       = 45,

  place        = {United States},

  year         = {2006},

  month        = {1}

}

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