Interaction of dioxygen with binuclear nitride-bridged iron porphyrins

David F. Bocian; Eric W. Findsen; Joseph A. Hofmann; G. Alan Schick; Daniel R. English; David N. Hendrickson; Kenneth S. Suslick

doi:10.1021/ic00175a003

Interaction of dioxygen with binuclear nitride-bridged iron porphyrins

David F. Bocian, Eric W. Findsen, Joseph A. Hofmann, G. Alan Schick, Daniel R. English, David N. Hendrickson, Kenneth S. Suslick

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Abstract

An unusual interaction between O₂ and nitride-bridged iron porphyrin dimers in frozen polar glasses has been found. The EPR spectrum previously attributed to a pyridine monoadduct of (μ-nitrido)bis[(5, 10, 15, 20-tetraphenylporphinato)iron] is in fact due to an O₂ adduct of the dimeric porphyrin. Optical spectroscopy shows that the O₂/porphyrin interaction is weak. Mossbauer spectra demonstrate that the two iron ions are inequivalent in the adduct while EPR data indicate a less anisotropic g tensor and appreciably diminished ¹⁴N and ⁵⁷Fe hyperfme coupling relative to the nonadducted species. O₂ titrations, as monitored by EPR, show that the adduct's stoichiometry is one ₂ per dimer. All these data are consistent with a weak axial interaction of O₂ with one side of the μ-nitrido dimer.

Original language	English (US)
Pages (from-to)	800-807
Number of pages	8
Journal	Inorganic Chemistry
Volume	23
Issue number	7
DOIs	https://doi.org/10.1021/ic00175a003
State	Published - Aug 1984

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Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Interaction of dioxygen with binuclear nitride-bridged iron porphyrins",

abstract = "An unusual interaction between O2 and nitride-bridged iron porphyrin dimers in frozen polar glasses has been found. The EPR spectrum previously attributed to a pyridine monoadduct of (μ-nitrido)bis[(5, 10, 15, 20-tetraphenylporphinato)iron] is in fact due to an O2 adduct of the dimeric porphyrin. Optical spectroscopy shows that the O2/porphyrin interaction is weak. Mossbauer spectra demonstrate that the two iron ions are inequivalent in the adduct while EPR data indicate a less anisotropic g tensor and appreciably diminished 14N and 57Fe hyperfme coupling relative to the nonadducted species. O2 titrations, as monitored by EPR, show that the adduct's stoichiometry is one 2 per dimer. All these data are consistent with a weak axial interaction of O2 with one side of the μ-nitrido dimer.",

author = "Bocian, {David F.} and Findsen, {Eric W.} and Hofmann, {Joseph A.} and {Alan Schick}, G. and English, {Daniel R.} and Hendrickson, {David N.} and Suslick, {Kenneth S.}",

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T1 - Interaction of dioxygen with binuclear nitride-bridged iron porphyrins

AU - Bocian, David F.

AU - Findsen, Eric W.

AU - Hofmann, Joseph A.

AU - Alan Schick, G.

AU - English, Daniel R.

AU - Hendrickson, David N.

AU - Suslick, Kenneth S.

PY - 1984/8

Y1 - 1984/8

N2 - An unusual interaction between O2 and nitride-bridged iron porphyrin dimers in frozen polar glasses has been found. The EPR spectrum previously attributed to a pyridine monoadduct of (μ-nitrido)bis[(5, 10, 15, 20-tetraphenylporphinato)iron] is in fact due to an O2 adduct of the dimeric porphyrin. Optical spectroscopy shows that the O2/porphyrin interaction is weak. Mossbauer spectra demonstrate that the two iron ions are inequivalent in the adduct while EPR data indicate a less anisotropic g tensor and appreciably diminished 14N and 57Fe hyperfme coupling relative to the nonadducted species. O2 titrations, as monitored by EPR, show that the adduct's stoichiometry is one 2 per dimer. All these data are consistent with a weak axial interaction of O2 with one side of the μ-nitrido dimer.

AB - An unusual interaction between O2 and nitride-bridged iron porphyrin dimers in frozen polar glasses has been found. The EPR spectrum previously attributed to a pyridine monoadduct of (μ-nitrido)bis[(5, 10, 15, 20-tetraphenylporphinato)iron] is in fact due to an O2 adduct of the dimeric porphyrin. Optical spectroscopy shows that the O2/porphyrin interaction is weak. Mossbauer spectra demonstrate that the two iron ions are inequivalent in the adduct while EPR data indicate a less anisotropic g tensor and appreciably diminished 14N and 57Fe hyperfme coupling relative to the nonadducted species. O2 titrations, as monitored by EPR, show that the adduct's stoichiometry is one 2 per dimer. All these data are consistent with a weak axial interaction of O2 with one side of the μ-nitrido dimer.

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Interaction of dioxygen with binuclear nitride-bridged iron porphyrins

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