Studies on mixed chelates-III. Mixed copper(II) chelates with N,N,N′,N′-tetramethylethylenediamine and β-diketones[1]

Yutaka Fukuda, Akiko Shimura, Masako Mukaida, Etsuko Fujita, Kozo Sone

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Abstract

A series of new mixed copper(II) chelates with N,N,N′,N′-tetramethylethylenediamine (TMEN) and various β-diketonate ions of the general formula [Cu TMEN(β-dik)] X. nH2O(β-dik = aca, bzaca, dbm, taa, hfa or dpm; X = ClO4 - or NO3 -; n = 1 2 or 0) were prepared. The magnetic moments, infrared spectra, and reflection spectra of their solids and the visible absorption spectra and electric conductivities of their organic solutions were measured, and the effects of the substituent groups in the β-diketonate ions, and those of the anions and solvents, on the electronic state and strengths of the coordinate bonds in the chelate cations were studied. The obtained results indicate that the magnitudes of ligand field splitting in these chelates strongly depend on the nature of the substituent groups, being particularly small in the chelates with fluorinated diketones. Further they show that there is a very obvious relation between these magnitudes and coordination abilities of the solvents expressed in their donor numbers. In most of the cases studied, ionization and solvation of the chelate cation of the type [Cu TMEN(β-dik)]X + 2S ⇄ [Cu TMEN (β-dik)S2]+ + X- (S = solvent molecule) seem to occur in organic solutions. However, in a highly non-polar solvent like 1,2-dichloroethane, anion coordination seems to occur.

Original languageEnglish
Pages (from-to)1265-1270
Number of pages6
JournalJournal of Inorganic and Nuclear Chemistry
Volume36
Issue number6
DOIs
Publication statusPublished - 1974

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chelates
Copper
copper
Anions
Cations
Negative ions
Positive ions
Ions
Solvation
anions
Electronic states
cations
Magnetic moments
Ionization
infrared reflection
Absorption spectra
visible spectrum
Ligands
solvation
Infrared radiation

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Studies on mixed chelates-III. Mixed copper(II) chelates with N,N,N′,N′-tetramethylethylenediamine and β-diketones[1]. / Fukuda, Yutaka; Shimura, Akiko; Mukaida, Masako; Fujita, Etsuko; Sone, Kozo.

In: Journal of Inorganic and Nuclear Chemistry, Vol. 36, No. 6, 1974, p. 1265-1270.

Research output: Contribution to journalArticle

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abstract = "A series of new mixed copper(II) chelates with N,N,N′,N′-tetramethylethylenediamine (TMEN) and various β-diketonate ions of the general formula [Cu TMEN(β-dik)] X. nH2O(β-dik = aca, bzaca, dbm, taa, hfa or dpm; X = ClO4 - or NO3 -; n = 1 2 or 0) were prepared. The magnetic moments, infrared spectra, and reflection spectra of their solids and the visible absorption spectra and electric conductivities of their organic solutions were measured, and the effects of the substituent groups in the β-diketonate ions, and those of the anions and solvents, on the electronic state and strengths of the coordinate bonds in the chelate cations were studied. The obtained results indicate that the magnitudes of ligand field splitting in these chelates strongly depend on the nature of the substituent groups, being particularly small in the chelates with fluorinated diketones. Further they show that there is a very obvious relation between these magnitudes and coordination abilities of the solvents expressed in their donor numbers. In most of the cases studied, ionization and solvation of the chelate cation of the type [Cu TMEN(β-dik)]X + 2S ⇄ [Cu TMEN (β-dik)S2]+ + X- (S = solvent molecule) seem to occur in organic solutions. However, in a highly non-polar solvent like 1,2-dichloroethane, anion coordination seems to occur.",
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N2 - A series of new mixed copper(II) chelates with N,N,N′,N′-tetramethylethylenediamine (TMEN) and various β-diketonate ions of the general formula [Cu TMEN(β-dik)] X. nH2O(β-dik = aca, bzaca, dbm, taa, hfa or dpm; X = ClO4 - or NO3 -; n = 1 2 or 0) were prepared. The magnetic moments, infrared spectra, and reflection spectra of their solids and the visible absorption spectra and electric conductivities of their organic solutions were measured, and the effects of the substituent groups in the β-diketonate ions, and those of the anions and solvents, on the electronic state and strengths of the coordinate bonds in the chelate cations were studied. The obtained results indicate that the magnitudes of ligand field splitting in these chelates strongly depend on the nature of the substituent groups, being particularly small in the chelates with fluorinated diketones. Further they show that there is a very obvious relation between these magnitudes and coordination abilities of the solvents expressed in their donor numbers. In most of the cases studied, ionization and solvation of the chelate cation of the type [Cu TMEN(β-dik)]X + 2S ⇄ [Cu TMEN (β-dik)S2]+ + X- (S = solvent molecule) seem to occur in organic solutions. However, in a highly non-polar solvent like 1,2-dichloroethane, anion coordination seems to occur.

AB - A series of new mixed copper(II) chelates with N,N,N′,N′-tetramethylethylenediamine (TMEN) and various β-diketonate ions of the general formula [Cu TMEN(β-dik)] X. nH2O(β-dik = aca, bzaca, dbm, taa, hfa or dpm; X = ClO4 - or NO3 -; n = 1 2 or 0) were prepared. The magnetic moments, infrared spectra, and reflection spectra of their solids and the visible absorption spectra and electric conductivities of their organic solutions were measured, and the effects of the substituent groups in the β-diketonate ions, and those of the anions and solvents, on the electronic state and strengths of the coordinate bonds in the chelate cations were studied. The obtained results indicate that the magnitudes of ligand field splitting in these chelates strongly depend on the nature of the substituent groups, being particularly small in the chelates with fluorinated diketones. Further they show that there is a very obvious relation between these magnitudes and coordination abilities of the solvents expressed in their donor numbers. In most of the cases studied, ionization and solvation of the chelate cation of the type [Cu TMEN(β-dik)]X + 2S ⇄ [Cu TMEN (β-dik)S2]+ + X- (S = solvent molecule) seem to occur in organic solutions. However, in a highly non-polar solvent like 1,2-dichloroethane, anion coordination seems to occur.

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