Quercetin 2,3-dioxygenase mimicking ring cleavage of the flavonolate ligand assisted by copper. Synthesis and characterization of copper(I) complexes [Cu(PPh3)2(fla)] (fla = flavonolate) and [Cu(PPh3)2(O-bs)] (O-bs = O-benzoylsalicylate)

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Abstract

Cu(PPh3)2(fla) has been prepared by reacting copper(I) chloride with sodium flavonolate in tetrahydrofuran solution. Crystallographic characterization of the complex (orthorhombic, P212121, a = 9.588(1) Å, b= 17.364(3) Å, c = 24.378(3) Å, V = 4058.6(10) Å3, Z = 4, R = 0.049) has shown that the coordination geometry of the molecule is tetrahedral. Oxygenation of Cu(PPh3)2(fla) in a methylene chloride solution at ambient conditions gives the O-benzoylsalicylato copper complex Cu(PPh3)2(O-bs) and carbon monoxide. Labeling experiments with an 18O216O2 mixture (1:4) evidenced the incorporation of both 18O atoms of 18O2 into the O-bs ligand. IR and MS studies of labeled O-bs confirmed the incorporation of 18O2 while the released CO remained unlabeled. Crystallographic characterization of Cu(PPh3)2(O-bs) on crystals obtained as the acetone solvate (triclinic, P1̄, a = 13.154(1) Å, b = 17.991(1) Å, c = 20.495(1) Å, a = 80.01(1)°, β= 88.02(1)°, γ = 71.83(1)°, V = 4537.5(5) Å3, Z = 4, R = 0.0403) shows that the molecule has a distorted tetrahedral structure. The oxygenolysis was followed by spectrophotometry, and the rate constants were determined according to the rate law - d[Cu(PPh3)2(fla)]/dt = fa[Cu(PPh3)2(fla)][O2]. The rate constant, activation enthalpy, and entropy at 363.16 K are as follows: k2/M-1 s-1 = 4.16 ± 0.48, ΔH/kJ mol-1 = 102 ±7, ΔS/J mol-1 K-1 = -13.0 ± 21. The reaction fits a Hammett linear free energy relationship for 4′-substituted flavonolates, and an increase of the electron density on copper makes the oxygenation reaction faster.

Original languageEnglish
Pages (from-to)3787-3795
Number of pages9
JournalInorganic Chemistry
Volume38
Issue number17
Publication statusPublished - 1999

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quercetin 2,3-dioxygenase
Oxygenation
Carbon Monoxide
Copper
cleavage
Rate constants
oxygenation
Ligands
copper
ligands
Molecules
Methylene Chloride
rings
Spectrophotometry
synthesis
Acetone
chlorides
Labeling
Free energy
Carrier concentration

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{f48c159d46184c92878fd24c220c9688,
title = "Quercetin 2,3-dioxygenase mimicking ring cleavage of the flavonolate ligand assisted by copper. Synthesis and characterization of copper(I) complexes [Cu(PPh3)2(fla)] (fla = flavonolate) and [Cu(PPh3)2(O-bs)] (O-bs = O-benzoylsalicylate)",
abstract = "Cu(PPh3)2(fla) has been prepared by reacting copper(I) chloride with sodium flavonolate in tetrahydrofuran solution. Crystallographic characterization of the complex (orthorhombic, P212121, a = 9.588(1) {\AA}, b= 17.364(3) {\AA}, c = 24.378(3) {\AA}, V = 4058.6(10) {\AA}3, Z = 4, R = 0.049) has shown that the coordination geometry of the molecule is tetrahedral. Oxygenation of Cu(PPh3)2(fla) in a methylene chloride solution at ambient conditions gives the O-benzoylsalicylato copper complex Cu(PPh3)2(O-bs) and carbon monoxide. Labeling experiments with an 18O216O2 mixture (1:4) evidenced the incorporation of both 18O atoms of 18O2 into the O-bs ligand. IR and MS studies of labeled O-bs confirmed the incorporation of 18O2 while the released CO remained unlabeled. Crystallographic characterization of Cu(PPh3)2(O-bs) on crystals obtained as the acetone solvate (triclinic, P1̄, a = 13.154(1) {\AA}, b = 17.991(1) {\AA}, c = 20.495(1) {\AA}, a = 80.01(1)°, β= 88.02(1)°, γ = 71.83(1)°, V = 4537.5(5) {\AA}3, Z = 4, R = 0.0403) shows that the molecule has a distorted tetrahedral structure. The oxygenolysis was followed by spectrophotometry, and the rate constants were determined according to the rate law - d[Cu(PPh3)2(fla)]/dt = fa[Cu(PPh3)2(fla)][O2]. The rate constant, activation enthalpy, and entropy at 363.16 K are as follows: k2/M-1 s-1 = 4.16 ± 0.48, ΔH‡/kJ mol-1 = 102 ±7, ΔS‡/J mol-1 K-1 = -13.0 ± 21. The reaction fits a Hammett linear free energy relationship for 4′-substituted flavonolates, and an increase of the electron density on copper makes the oxygenation reaction faster.",
author = "E. Balogh-Hergovich and J. Kaizer and G. Speier and Vilmos F{\"u}l{\"o}p and L. P{\'a}rk{\'a}ny{\'i}",
year = "1999",
language = "English",
volume = "38",
pages = "3787--3795",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "17",

}

TY - JOUR

T1 - Quercetin 2,3-dioxygenase mimicking ring cleavage of the flavonolate ligand assisted by copper. Synthesis and characterization of copper(I) complexes [Cu(PPh3)2(fla)] (fla = flavonolate) and [Cu(PPh3)2(O-bs)] (O-bs = O-benzoylsalicylate)

AU - Balogh-Hergovich, E.

AU - Kaizer, J.

AU - Speier, G.

AU - Fülöp, Vilmos

AU - Párkányí, L.

PY - 1999

Y1 - 1999

N2 - Cu(PPh3)2(fla) has been prepared by reacting copper(I) chloride with sodium flavonolate in tetrahydrofuran solution. Crystallographic characterization of the complex (orthorhombic, P212121, a = 9.588(1) Å, b= 17.364(3) Å, c = 24.378(3) Å, V = 4058.6(10) Å3, Z = 4, R = 0.049) has shown that the coordination geometry of the molecule is tetrahedral. Oxygenation of Cu(PPh3)2(fla) in a methylene chloride solution at ambient conditions gives the O-benzoylsalicylato copper complex Cu(PPh3)2(O-bs) and carbon monoxide. Labeling experiments with an 18O216O2 mixture (1:4) evidenced the incorporation of both 18O atoms of 18O2 into the O-bs ligand. IR and MS studies of labeled O-bs confirmed the incorporation of 18O2 while the released CO remained unlabeled. Crystallographic characterization of Cu(PPh3)2(O-bs) on crystals obtained as the acetone solvate (triclinic, P1̄, a = 13.154(1) Å, b = 17.991(1) Å, c = 20.495(1) Å, a = 80.01(1)°, β= 88.02(1)°, γ = 71.83(1)°, V = 4537.5(5) Å3, Z = 4, R = 0.0403) shows that the molecule has a distorted tetrahedral structure. The oxygenolysis was followed by spectrophotometry, and the rate constants were determined according to the rate law - d[Cu(PPh3)2(fla)]/dt = fa[Cu(PPh3)2(fla)][O2]. The rate constant, activation enthalpy, and entropy at 363.16 K are as follows: k2/M-1 s-1 = 4.16 ± 0.48, ΔH‡/kJ mol-1 = 102 ±7, ΔS‡/J mol-1 K-1 = -13.0 ± 21. The reaction fits a Hammett linear free energy relationship for 4′-substituted flavonolates, and an increase of the electron density on copper makes the oxygenation reaction faster.

AB - Cu(PPh3)2(fla) has been prepared by reacting copper(I) chloride with sodium flavonolate in tetrahydrofuran solution. Crystallographic characterization of the complex (orthorhombic, P212121, a = 9.588(1) Å, b= 17.364(3) Å, c = 24.378(3) Å, V = 4058.6(10) Å3, Z = 4, R = 0.049) has shown that the coordination geometry of the molecule is tetrahedral. Oxygenation of Cu(PPh3)2(fla) in a methylene chloride solution at ambient conditions gives the O-benzoylsalicylato copper complex Cu(PPh3)2(O-bs) and carbon monoxide. Labeling experiments with an 18O216O2 mixture (1:4) evidenced the incorporation of both 18O atoms of 18O2 into the O-bs ligand. IR and MS studies of labeled O-bs confirmed the incorporation of 18O2 while the released CO remained unlabeled. Crystallographic characterization of Cu(PPh3)2(O-bs) on crystals obtained as the acetone solvate (triclinic, P1̄, a = 13.154(1) Å, b = 17.991(1) Å, c = 20.495(1) Å, a = 80.01(1)°, β= 88.02(1)°, γ = 71.83(1)°, V = 4537.5(5) Å3, Z = 4, R = 0.0403) shows that the molecule has a distorted tetrahedral structure. The oxygenolysis was followed by spectrophotometry, and the rate constants were determined according to the rate law - d[Cu(PPh3)2(fla)]/dt = fa[Cu(PPh3)2(fla)][O2]. The rate constant, activation enthalpy, and entropy at 363.16 K are as follows: k2/M-1 s-1 = 4.16 ± 0.48, ΔH‡/kJ mol-1 = 102 ±7, ΔS‡/J mol-1 K-1 = -13.0 ± 21. The reaction fits a Hammett linear free energy relationship for 4′-substituted flavonolates, and an increase of the electron density on copper makes the oxygenation reaction faster.

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