5,10,15,20-Tetrakis(α,α,α,α-o-pivalamidophenyl) porphinatoiron(II) bearing a covalently linked axial imidazole via m-aminobenzoic acid. Synthesis and influence of imidazole basicity on O2-binding affinity

Teruyuki Komatsu, Yuka Furubayashi, Hiroyuki Nishide, Eishun Tsuchida

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

A 5,10,15,20-tetrakis(α,α,α,α-o-pivalamidophenyl) porphinatoiron(II) derivative bearing a covalently linked axial imidazole via a rigid benzoyloxy spacer (8c) has been synthesized. The O- 2 and CO-binding affinities of 8c (PO2 1/2: 213 Torr, PCO 1/2: 0.17 Torr in toluene at 25°C) were significantly lower than those of a similar analog having a flexible ω-imidazolylalkyl group (9c). Kinetically, the low binding affinities of these gaseous molecules are attributed to the high dissociation rate constants. The stretching frequency of the CO bound to the central Fe(II), however, showed exactly the same value (vCO: 1964 cm-1) for both complexes. These results suggested that the intramolecular imidazole coordination was not disordered by the rigid benzoyloxy spacer in 8c. We concluded that the low O- 2 and CO-binding affinities of 8c were caused by the low σ-basicity (pKa) of the imidazole ring.

Original languageEnglish
Pages (from-to)234-238
Number of pages5
JournalInorganica Chimica Acta
Volume295
Issue number2
Publication statusPublished - 1999 Nov 30

Fingerprint

Bearings (structural)
Carbon Monoxide
Alkalinity
imidazoles
Stretching
Toluene
affinity
Rate constants
Derivatives
spacers
acids
Molecules
Acids
synthesis
toluene
dissociation
analogs
rings
3-aminobenzoic acid
imidazole

Keywords

  • Benzoyloxy spacer
  • Imidazole basicity
  • Iron(II) complexes
  • O-Binding affinity
  • Porphinatoiron(II) derivative

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

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title = "5,10,15,20-Tetrakis(α,α,α,α-o-pivalamidophenyl) porphinatoiron(II) bearing a covalently linked axial imidazole via m-aminobenzoic acid. Synthesis and influence of imidazole basicity on O2-binding affinity",
abstract = "A 5,10,15,20-tetrakis(α,α,α,α-o-pivalamidophenyl) porphinatoiron(II) derivative bearing a covalently linked axial imidazole via a rigid benzoyloxy spacer (8c) has been synthesized. The O- 2 and CO-binding affinities of 8c (PO2 1/2: 213 Torr, PCO 1/2: 0.17 Torr in toluene at 25°C) were significantly lower than those of a similar analog having a flexible ω-imidazolylalkyl group (9c). Kinetically, the low binding affinities of these gaseous molecules are attributed to the high dissociation rate constants. The stretching frequency of the CO bound to the central Fe(II), however, showed exactly the same value (vCO: 1964 cm-1) for both complexes. These results suggested that the intramolecular imidazole coordination was not disordered by the rigid benzoyloxy spacer in 8c. We concluded that the low O- 2 and CO-binding affinities of 8c were caused by the low σ-basicity (pKa) of the imidazole ring.",
keywords = "Benzoyloxy spacer, Imidazole basicity, Iron(II) complexes, O-Binding affinity, Porphinatoiron(II) derivative",
author = "Teruyuki Komatsu and Yuka Furubayashi and Hiroyuki Nishide and Eishun Tsuchida",
year = "1999",
month = "11",
day = "30",
language = "English",
volume = "295",
pages = "234--238",
journal = "Inorganica Chimica Acta",
issn = "0020-1693",
publisher = "Elsevier BV",
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TY - JOUR

T1 - 5,10,15,20-Tetrakis(α,α,α,α-o-pivalamidophenyl) porphinatoiron(II) bearing a covalently linked axial imidazole via m-aminobenzoic acid. Synthesis and influence of imidazole basicity on O2-binding affinity

AU - Komatsu, Teruyuki

AU - Furubayashi, Yuka

AU - Nishide, Hiroyuki

AU - Tsuchida, Eishun

PY - 1999/11/30

Y1 - 1999/11/30

N2 - A 5,10,15,20-tetrakis(α,α,α,α-o-pivalamidophenyl) porphinatoiron(II) derivative bearing a covalently linked axial imidazole via a rigid benzoyloxy spacer (8c) has been synthesized. The O- 2 and CO-binding affinities of 8c (PO2 1/2: 213 Torr, PCO 1/2: 0.17 Torr in toluene at 25°C) were significantly lower than those of a similar analog having a flexible ω-imidazolylalkyl group (9c). Kinetically, the low binding affinities of these gaseous molecules are attributed to the high dissociation rate constants. The stretching frequency of the CO bound to the central Fe(II), however, showed exactly the same value (vCO: 1964 cm-1) for both complexes. These results suggested that the intramolecular imidazole coordination was not disordered by the rigid benzoyloxy spacer in 8c. We concluded that the low O- 2 and CO-binding affinities of 8c were caused by the low σ-basicity (pKa) of the imidazole ring.

AB - A 5,10,15,20-tetrakis(α,α,α,α-o-pivalamidophenyl) porphinatoiron(II) derivative bearing a covalently linked axial imidazole via a rigid benzoyloxy spacer (8c) has been synthesized. The O- 2 and CO-binding affinities of 8c (PO2 1/2: 213 Torr, PCO 1/2: 0.17 Torr in toluene at 25°C) were significantly lower than those of a similar analog having a flexible ω-imidazolylalkyl group (9c). Kinetically, the low binding affinities of these gaseous molecules are attributed to the high dissociation rate constants. The stretching frequency of the CO bound to the central Fe(II), however, showed exactly the same value (vCO: 1964 cm-1) for both complexes. These results suggested that the intramolecular imidazole coordination was not disordered by the rigid benzoyloxy spacer in 8c. We concluded that the low O- 2 and CO-binding affinities of 8c were caused by the low σ-basicity (pKa) of the imidazole ring.

KW - Benzoyloxy spacer

KW - Imidazole basicity

KW - Iron(II) complexes

KW - O-Binding affinity

KW - Porphinatoiron(II) derivative

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