Oxomanganese(IV) Porphyrins Identified by Resonance Raman and Infrared Spectroscopy: Weak Bonds and the Stability of the Half-Filled t2g Subshell

Roman S. Czernuszewicz, Michael K. Stern, Kathleen A. Macor, Dongho Kim, John T. Groves, Thomas G. Spiro, Y. Oliver Su

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Abstract

The MnIV-O stretching frequency is identified at 754 cm -1 in resonance Raman (RR) and infrared (IR) spectra of MnIV porphyrins prepared by electrooxidation of ClMnIIITMP (TMP = tetramesitylporphyrin), ClMnIIITPP (TPP = tetraphenylporphyrin) and ClMnIIIOEP (OEP = octaethylporphyrin) in CH3CN containing tetrabutylammonium hydroxide (TBA(OH)). This vibrational band establishes oxo-MnIV bond formation under these conditions and shows the bond to be anomalously weak. When the oxidation is carried out in CH2C12 containing TBA(OH), or when ClMnIIITMPyP (TMPyP = tetrakis(methylpyridinium)porphyrin) is electrooxidized in aqueous 1 M NaOH, the Mn-O stretching band is seen at 711 cm-1. This band is associated with a trans OH- adduct, as shown by its anomalous upshift, to 732 cm-1, in D2O; the lower frequency in H2O is attributed to interaction with the Mn-O-H bend of the trans OH- ligand, which is relieved when H is replaced by D. EPR spectra of all these species show strong g~ 4.0 and weak g~ 2.0 signals characteristic of a high-spin d3 configuration. The MnIIITMPyP species in 1 M NaOH is shown to be a trans dihydroxide adduct by virtue of a 495-cm-1 RR band identified, on the basis of its H218O and D2O shifts, as the symmetric Mn-(OH)2 stretch. The M-O stretching frequencies are compared for VIV, CrIV, MnIV, and FeIV porphyrins, and the anomalous weakness of the MnIV-O bond is attributed to the special stability and low polarizability of the half-filled t32g subshell. Consequences of this weak bond for manganyl reactivity are discussed.

Original languageEnglish
Pages (from-to)4158-4165
Number of pages8
JournalJournal of the American Chemical Society
Volume110
Issue number13
DOIs
Publication statusPublished - 1988 Jan 1

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Raman Spectrum Analysis
Porphyrins
Stretching
Raman spectroscopy
Infrared spectroscopy
Thymidine Monophosphate
Electrooxidation
Paramagnetic resonance
Ligands
Infrared radiation
Oxidation
hydroxide ion

All Science Journal Classification (ASJC) codes

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

Cite this

Czernuszewicz, Roman S. ; Stern, Michael K. ; Macor, Kathleen A. ; Kim, Dongho ; Groves, John T. ; Spiro, Thomas G. ; Su, Y. Oliver. / Oxomanganese(IV) Porphyrins Identified by Resonance Raman and Infrared Spectroscopy : Weak Bonds and the Stability of the Half-Filled t2g Subshell. In: Journal of the American Chemical Society. 1988 ; Vol. 110, No. 13. pp. 4158-4165.
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abstract = "The MnIV-O stretching frequency is identified at 754 cm -1 in resonance Raman (RR) and infrared (IR) spectra of MnIV porphyrins prepared by electrooxidation of ClMnIIITMP (TMP = tetramesitylporphyrin), ClMnIIITPP (TPP = tetraphenylporphyrin) and ClMnIIIOEP (OEP = octaethylporphyrin) in CH3CN containing tetrabutylammonium hydroxide (TBA(OH)). This vibrational band establishes oxo-MnIV bond formation under these conditions and shows the bond to be anomalously weak. When the oxidation is carried out in CH2C12 containing TBA(OH), or when ClMnIIITMPyP (TMPyP = tetrakis(methylpyridinium)porphyrin) is electrooxidized in aqueous 1 M NaOH, the Mn-O stretching band is seen at 711 cm-1. This band is associated with a trans OH- adduct, as shown by its anomalous upshift, to 732 cm-1, in D2O; the lower frequency in H2O is attributed to interaction with the Mn-O-H bend of the trans OH- ligand, which is relieved when H is replaced by D. EPR spectra of all these species show strong g⊥~ 4.0 and weak g∥~ 2.0 signals characteristic of a high-spin d3 configuration. The MnIIITMPyP species in 1 M NaOH is shown to be a trans dihydroxide adduct by virtue of a 495-cm-1 RR band identified, on the basis of its H218O and D2O shifts, as the symmetric Mn-(OH)2 stretch. The M-O stretching frequencies are compared for VIV, CrIV, MnIV, and FeIV porphyrins, and the anomalous weakness of the MnIV-O bond is attributed to the special stability and low polarizability of the half-filled t32g subshell. Consequences of this weak bond for manganyl reactivity are discussed.",
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Oxomanganese(IV) Porphyrins Identified by Resonance Raman and Infrared Spectroscopy : Weak Bonds and the Stability of the Half-Filled t2g Subshell. / Czernuszewicz, Roman S.; Stern, Michael K.; Macor, Kathleen A.; Kim, Dongho; Groves, John T.; Spiro, Thomas G.; Su, Y. Oliver.

In: Journal of the American Chemical Society, Vol. 110, No. 13, 01.01.1988, p. 4158-4165.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Oxomanganese(IV) Porphyrins Identified by Resonance Raman and Infrared Spectroscopy

T2 - Weak Bonds and the Stability of the Half-Filled t2g Subshell

AU - Czernuszewicz, Roman S.

AU - Stern, Michael K.

AU - Macor, Kathleen A.

AU - Kim, Dongho

AU - Groves, John T.

AU - Spiro, Thomas G.

AU - Su, Y. Oliver

PY - 1988/1/1

Y1 - 1988/1/1

N2 - The MnIV-O stretching frequency is identified at 754 cm -1 in resonance Raman (RR) and infrared (IR) spectra of MnIV porphyrins prepared by electrooxidation of ClMnIIITMP (TMP = tetramesitylporphyrin), ClMnIIITPP (TPP = tetraphenylporphyrin) and ClMnIIIOEP (OEP = octaethylporphyrin) in CH3CN containing tetrabutylammonium hydroxide (TBA(OH)). This vibrational band establishes oxo-MnIV bond formation under these conditions and shows the bond to be anomalously weak. When the oxidation is carried out in CH2C12 containing TBA(OH), or when ClMnIIITMPyP (TMPyP = tetrakis(methylpyridinium)porphyrin) is electrooxidized in aqueous 1 M NaOH, the Mn-O stretching band is seen at 711 cm-1. This band is associated with a trans OH- adduct, as shown by its anomalous upshift, to 732 cm-1, in D2O; the lower frequency in H2O is attributed to interaction with the Mn-O-H bend of the trans OH- ligand, which is relieved when H is replaced by D. EPR spectra of all these species show strong g⊥~ 4.0 and weak g∥~ 2.0 signals characteristic of a high-spin d3 configuration. The MnIIITMPyP species in 1 M NaOH is shown to be a trans dihydroxide adduct by virtue of a 495-cm-1 RR band identified, on the basis of its H218O and D2O shifts, as the symmetric Mn-(OH)2 stretch. The M-O stretching frequencies are compared for VIV, CrIV, MnIV, and FeIV porphyrins, and the anomalous weakness of the MnIV-O bond is attributed to the special stability and low polarizability of the half-filled t32g subshell. Consequences of this weak bond for manganyl reactivity are discussed.

AB - The MnIV-O stretching frequency is identified at 754 cm -1 in resonance Raman (RR) and infrared (IR) spectra of MnIV porphyrins prepared by electrooxidation of ClMnIIITMP (TMP = tetramesitylporphyrin), ClMnIIITPP (TPP = tetraphenylporphyrin) and ClMnIIIOEP (OEP = octaethylporphyrin) in CH3CN containing tetrabutylammonium hydroxide (TBA(OH)). This vibrational band establishes oxo-MnIV bond formation under these conditions and shows the bond to be anomalously weak. When the oxidation is carried out in CH2C12 containing TBA(OH), or when ClMnIIITMPyP (TMPyP = tetrakis(methylpyridinium)porphyrin) is electrooxidized in aqueous 1 M NaOH, the Mn-O stretching band is seen at 711 cm-1. This band is associated with a trans OH- adduct, as shown by its anomalous upshift, to 732 cm-1, in D2O; the lower frequency in H2O is attributed to interaction with the Mn-O-H bend of the trans OH- ligand, which is relieved when H is replaced by D. EPR spectra of all these species show strong g⊥~ 4.0 and weak g∥~ 2.0 signals characteristic of a high-spin d3 configuration. The MnIIITMPyP species in 1 M NaOH is shown to be a trans dihydroxide adduct by virtue of a 495-cm-1 RR band identified, on the basis of its H218O and D2O shifts, as the symmetric Mn-(OH)2 stretch. The M-O stretching frequencies are compared for VIV, CrIV, MnIV, and FeIV porphyrins, and the anomalous weakness of the MnIV-O bond is attributed to the special stability and low polarizability of the half-filled t32g subshell. Consequences of this weak bond for manganyl reactivity are discussed.

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