Highly variable π-bonding in the interaction of iron(II) porphyrinates with nitrite

H. Nasri, M. K. Ellison, Carsten Krebs, B. H. Huynh, W. R. Scheidt

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Abstract

The reaction of the four-coordinate picket fence iron(II) porphyrin complex [Fe(TpivPP)] with cryptand-solubilized KNO2 yields the five-coordinate porphyrin species [Fe(TpivPP)(NO2)]-. The six-coordinate complexes, [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]-, are obtained when pentamethylene sulfide or pyridine is added anaerobically to the preformed five-coordinate porphyrin species. These novel species are characterized by UV-vis, IR, and Mossbauer spectroscopies as well as single-crystal structure determinations. The Mossbauer investigation shows that the isomer shifts and quadrupole splittings for [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]- are typical for six-coordinate, low-spin (S = 0) iron(II) porphyrinate complexes. This is in distinct contrast to the unusually large quadrupole splitting of the five-coordinate species [Fe(TpivPP)(NO2)]-. The molecular structures of [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]- show that the nitro groups are inside the 'pocket' of the porphyrin trans to the neutral sulfur- or nitrogen-donating axial ligand. In all species, the projection of the nitrite ion onto the porphyrin plane bisects a N(p) -Fe-N(p) angle. In the pyridine derivative, the dihedral angle between the two axial ligand planes is 81.4°. In the pentamethylene sulfide derivative, Fe-N(p) = 1.990(6) Å, Fe-N(NO2) = 1.937(3) Å, and Fe-S(PMS) = 2.380(2) Å, while in the pyridine derivative Fe-N(p) = 1.990(15) Å, Fe-N(NO2) = 1.951(5) Å, and Fe-N(Py) = 2.032(5) Å. In [Fe(TpivPP)(NO2)]-, Fe-N(p) is 1.970(4) Å while Fe-N(NO2) is a very short 1.849(6) Å. The structural and spectroscopic data are interpreted as showing a significant difference in the [Fe-NO2] π interaction on change in coordination number.

Original languageEnglish (US)
Pages (from-to)10795-10804
Number of pages10
JournalJournal of the American Chemical Society
Volume122
Issue number44
DOIs
StatePublished - Nov 8 2000

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Porphyrins
Nitrites
Iron
Pyridine
Sulfides
Derivatives
Ligands
Mossbauer Spectroscopy
Fences
Mossbauer spectroscopy
Dihedral angle
Molecular Structure
Ultraviolet spectroscopy
Sulfur
Isomers
Molecular structure
Infrared spectroscopy
Nitrogen
Crystal structure
Single crystals

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Nasri, H. ; Ellison, M. K. ; Krebs, Carsten ; Huynh, B. H. ; Scheidt, W. R. / Highly variable π-bonding in the interaction of iron(II) porphyrinates with nitrite. In: Journal of the American Chemical Society. 2000 ; Vol. 122, No. 44. pp. 10795-10804.
@article{f6ec454afe4c444982905297d984009c,
title = "Highly variable π-bonding in the interaction of iron(II) porphyrinates with nitrite",
abstract = "The reaction of the four-coordinate picket fence iron(II) porphyrin complex [Fe(TpivPP)] with cryptand-solubilized KNO2 yields the five-coordinate porphyrin species [Fe(TpivPP)(NO2)]-. The six-coordinate complexes, [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]-, are obtained when pentamethylene sulfide or pyridine is added anaerobically to the preformed five-coordinate porphyrin species. These novel species are characterized by UV-vis, IR, and Mossbauer spectroscopies as well as single-crystal structure determinations. The Mossbauer investigation shows that the isomer shifts and quadrupole splittings for [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]- are typical for six-coordinate, low-spin (S = 0) iron(II) porphyrinate complexes. This is in distinct contrast to the unusually large quadrupole splitting of the five-coordinate species [Fe(TpivPP)(NO2)]-. The molecular structures of [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]- show that the nitro groups are inside the 'pocket' of the porphyrin trans to the neutral sulfur- or nitrogen-donating axial ligand. In all species, the projection of the nitrite ion onto the porphyrin plane bisects a N(p) -Fe-N(p) angle. In the pyridine derivative, the dihedral angle between the two axial ligand planes is 81.4°. In the pentamethylene sulfide derivative, Fe-N(p) = 1.990(6) {\AA}, Fe-N(NO2) = 1.937(3) {\AA}, and Fe-S(PMS) = 2.380(2) {\AA}, while in the pyridine derivative Fe-N(p) = 1.990(15) {\AA}, Fe-N(NO2) = 1.951(5) {\AA}, and Fe-N(Py) = 2.032(5) {\AA}. In [Fe(TpivPP)(NO2)]-, Fe-N(p) is 1.970(4) {\AA} while Fe-N(NO2) is a very short 1.849(6) {\AA}. The structural and spectroscopic data are interpreted as showing a significant difference in the [Fe-NO2] π interaction on change in coordination number.",
author = "H. Nasri and Ellison, {M. K.} and Carsten Krebs and Huynh, {B. H.} and Scheidt, {W. R.}",
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Highly variable π-bonding in the interaction of iron(II) porphyrinates with nitrite. / Nasri, H.; Ellison, M. K.; Krebs, Carsten; Huynh, B. H.; Scheidt, W. R.

In: Journal of the American Chemical Society, Vol. 122, No. 44, 08.11.2000, p. 10795-10804.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Highly variable π-bonding in the interaction of iron(II) porphyrinates with nitrite

AU - Nasri, H.

AU - Ellison, M. K.

AU - Krebs, Carsten

AU - Huynh, B. H.

AU - Scheidt, W. R.

PY - 2000/11/8

Y1 - 2000/11/8

N2 - The reaction of the four-coordinate picket fence iron(II) porphyrin complex [Fe(TpivPP)] with cryptand-solubilized KNO2 yields the five-coordinate porphyrin species [Fe(TpivPP)(NO2)]-. The six-coordinate complexes, [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]-, are obtained when pentamethylene sulfide or pyridine is added anaerobically to the preformed five-coordinate porphyrin species. These novel species are characterized by UV-vis, IR, and Mossbauer spectroscopies as well as single-crystal structure determinations. The Mossbauer investigation shows that the isomer shifts and quadrupole splittings for [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]- are typical for six-coordinate, low-spin (S = 0) iron(II) porphyrinate complexes. This is in distinct contrast to the unusually large quadrupole splitting of the five-coordinate species [Fe(TpivPP)(NO2)]-. The molecular structures of [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]- show that the nitro groups are inside the 'pocket' of the porphyrin trans to the neutral sulfur- or nitrogen-donating axial ligand. In all species, the projection of the nitrite ion onto the porphyrin plane bisects a N(p) -Fe-N(p) angle. In the pyridine derivative, the dihedral angle between the two axial ligand planes is 81.4°. In the pentamethylene sulfide derivative, Fe-N(p) = 1.990(6) Å, Fe-N(NO2) = 1.937(3) Å, and Fe-S(PMS) = 2.380(2) Å, while in the pyridine derivative Fe-N(p) = 1.990(15) Å, Fe-N(NO2) = 1.951(5) Å, and Fe-N(Py) = 2.032(5) Å. In [Fe(TpivPP)(NO2)]-, Fe-N(p) is 1.970(4) Å while Fe-N(NO2) is a very short 1.849(6) Å. The structural and spectroscopic data are interpreted as showing a significant difference in the [Fe-NO2] π interaction on change in coordination number.

AB - The reaction of the four-coordinate picket fence iron(II) porphyrin complex [Fe(TpivPP)] with cryptand-solubilized KNO2 yields the five-coordinate porphyrin species [Fe(TpivPP)(NO2)]-. The six-coordinate complexes, [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]-, are obtained when pentamethylene sulfide or pyridine is added anaerobically to the preformed five-coordinate porphyrin species. These novel species are characterized by UV-vis, IR, and Mossbauer spectroscopies as well as single-crystal structure determinations. The Mossbauer investigation shows that the isomer shifts and quadrupole splittings for [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]- are typical for six-coordinate, low-spin (S = 0) iron(II) porphyrinate complexes. This is in distinct contrast to the unusually large quadrupole splitting of the five-coordinate species [Fe(TpivPP)(NO2)]-. The molecular structures of [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]- show that the nitro groups are inside the 'pocket' of the porphyrin trans to the neutral sulfur- or nitrogen-donating axial ligand. In all species, the projection of the nitrite ion onto the porphyrin plane bisects a N(p) -Fe-N(p) angle. In the pyridine derivative, the dihedral angle between the two axial ligand planes is 81.4°. In the pentamethylene sulfide derivative, Fe-N(p) = 1.990(6) Å, Fe-N(NO2) = 1.937(3) Å, and Fe-S(PMS) = 2.380(2) Å, while in the pyridine derivative Fe-N(p) = 1.990(15) Å, Fe-N(NO2) = 1.951(5) Å, and Fe-N(Py) = 2.032(5) Å. In [Fe(TpivPP)(NO2)]-, Fe-N(p) is 1.970(4) Å while Fe-N(NO2) is a very short 1.849(6) Å. The structural and spectroscopic data are interpreted as showing a significant difference in the [Fe-NO2] π interaction on change in coordination number.

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