Kinetic studies on the copper(II)-mediated oxygenolysis of the flavonolate ligand. Crystal structures of [Cu(fla)2] (fla = flavonolate) and [Cu(O-bs)2(py)3] (O-bs = O-benzoylsalicylate)

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Abstract

The complex [Cu(fla)2] has been prepared by treating copper(n) chloride with sodium flavonolate in tetrahydrofuran solution. Crystallographic characterisation of the complex [Cu(fla)2]·2CHCl3 has shown that the co-ordination geometry around the copper(II) ion is square planar. Oxygenation of [Cu(fla)2] in dimethylformamide solution at ambient conditions gives [Cu(O-bs)2] (O-bs = O-benzoylsalicylate) and carbon monoxide. Crystallographic characterisation of [Cu(O-bs)2] on crystals obtained from pyridine as [Cu(O-bs)2(py)3]·0.91py revealed that the coordination geometry of the copper(n) ion is square pyramidal with trans O atoms of O-bs and N atoms of py ligands in basal and an N atom of py in apical position. The oxygenolysis of [Cu(fla)2] in DMF was followed by electron spectroscopy and the rate constants were determined according to the rate law -d[Cu(fla)2]/dt = k[Cu(fla)2][O2]. The rate constant, activation enthalpy, entropy and free energy at 373 K are as follows: k/mol dm-3s-1 = (1.57 ± 0.08) × 10-2, ΔH/kJ mol-1 = 53 ± 6, ΔS/J K-1 mol-1 = -138 ± 11, ΔG/kJ mol-1 = 105 ± 2. The reaction fits a Hammett linear free energy relationship and a higher electron density on copper results in a faster oxygenation reaction.

Original languageEnglish
Pages (from-to)3847-3854
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number21
Publication statusPublished - Nov 7 1999

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Copper
Crystal structure
Ligands
Kinetics
Oxygenation
Atoms
Free energy
Rate constants
Ions
Dimethylformamide
Electron spectroscopy
Geometry
Carbon Monoxide
Carrier concentration
Chlorides
Enthalpy
Entropy
Sodium
Chemical activation
Crystals

ASJC Scopus subject areas

  • Inorganic Chemistry

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title = "Kinetic studies on the copper(II)-mediated oxygenolysis of the flavonolate ligand. Crystal structures of [Cu(fla)2] (fla = flavonolate) and [Cu(O-bs)2(py)3] (O-bs = O-benzoylsalicylate)",
abstract = "The complex [Cu(fla)2] has been prepared by treating copper(n) chloride with sodium flavonolate in tetrahydrofuran solution. Crystallographic characterisation of the complex [Cu(fla)2]·2CHCl3 has shown that the co-ordination geometry around the copper(II) ion is square planar. Oxygenation of [Cu(fla)2] in dimethylformamide solution at ambient conditions gives [Cu(O-bs)2] (O-bs = O-benzoylsalicylate) and carbon monoxide. Crystallographic characterisation of [Cu(O-bs)2] on crystals obtained from pyridine as [Cu(O-bs)2(py)3]·0.91py revealed that the coordination geometry of the copper(n) ion is square pyramidal with trans O atoms of O-bs and N atoms of py ligands in basal and an N atom of py in apical position. The oxygenolysis of [Cu(fla)2] in DMF was followed by electron spectroscopy and the rate constants were determined according to the rate law -d[Cu(fla)2]/dt = k[Cu(fla)2][O2]. The rate constant, activation enthalpy, entropy and free energy at 373 K are as follows: k/mol dm-3s-1 = (1.57 ± 0.08) × 10-2, ΔH‡/kJ mol-1 = 53 ± 6, ΔS‡/J K-1 mol-1 = -138 ± 11, ΔG‡/kJ mol-1 = 105 ± 2. The reaction fits a Hammett linear free energy relationship and a higher electron density on copper results in a faster oxygenation reaction.",
author = "E. Balogh-Hergovich and J. Kaizer and G. Speier and G. Argay and L. P{\'a}rk{\'a}ny{\'i}",
year = "1999",
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language = "English",
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T1 - Kinetic studies on the copper(II)-mediated oxygenolysis of the flavonolate ligand. Crystal structures of [Cu(fla)2] (fla = flavonolate) and [Cu(O-bs)2(py)3] (O-bs = O-benzoylsalicylate)

AU - Balogh-Hergovich, E.

AU - Kaizer, J.

AU - Speier, G.

AU - Argay, G.

AU - Párkányí, L.

PY - 1999/11/7

Y1 - 1999/11/7

N2 - The complex [Cu(fla)2] has been prepared by treating copper(n) chloride with sodium flavonolate in tetrahydrofuran solution. Crystallographic characterisation of the complex [Cu(fla)2]·2CHCl3 has shown that the co-ordination geometry around the copper(II) ion is square planar. Oxygenation of [Cu(fla)2] in dimethylformamide solution at ambient conditions gives [Cu(O-bs)2] (O-bs = O-benzoylsalicylate) and carbon monoxide. Crystallographic characterisation of [Cu(O-bs)2] on crystals obtained from pyridine as [Cu(O-bs)2(py)3]·0.91py revealed that the coordination geometry of the copper(n) ion is square pyramidal with trans O atoms of O-bs and N atoms of py ligands in basal and an N atom of py in apical position. The oxygenolysis of [Cu(fla)2] in DMF was followed by electron spectroscopy and the rate constants were determined according to the rate law -d[Cu(fla)2]/dt = k[Cu(fla)2][O2]. The rate constant, activation enthalpy, entropy and free energy at 373 K are as follows: k/mol dm-3s-1 = (1.57 ± 0.08) × 10-2, ΔH‡/kJ mol-1 = 53 ± 6, ΔS‡/J K-1 mol-1 = -138 ± 11, ΔG‡/kJ mol-1 = 105 ± 2. The reaction fits a Hammett linear free energy relationship and a higher electron density on copper results in a faster oxygenation reaction.

AB - The complex [Cu(fla)2] has been prepared by treating copper(n) chloride with sodium flavonolate in tetrahydrofuran solution. Crystallographic characterisation of the complex [Cu(fla)2]·2CHCl3 has shown that the co-ordination geometry around the copper(II) ion is square planar. Oxygenation of [Cu(fla)2] in dimethylformamide solution at ambient conditions gives [Cu(O-bs)2] (O-bs = O-benzoylsalicylate) and carbon monoxide. Crystallographic characterisation of [Cu(O-bs)2] on crystals obtained from pyridine as [Cu(O-bs)2(py)3]·0.91py revealed that the coordination geometry of the copper(n) ion is square pyramidal with trans O atoms of O-bs and N atoms of py ligands in basal and an N atom of py in apical position. The oxygenolysis of [Cu(fla)2] in DMF was followed by electron spectroscopy and the rate constants were determined according to the rate law -d[Cu(fla)2]/dt = k[Cu(fla)2][O2]. The rate constant, activation enthalpy, entropy and free energy at 373 K are as follows: k/mol dm-3s-1 = (1.57 ± 0.08) × 10-2, ΔH‡/kJ mol-1 = 53 ± 6, ΔS‡/J K-1 mol-1 = -138 ± 11, ΔG‡/kJ mol-1 = 105 ± 2. The reaction fits a Hammett linear free energy relationship and a higher electron density on copper results in a faster oxygenation reaction.

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