Preparation, structure, and spectroscopy of cobalt(III) complexes containing N,N′-di-8-quinolyl derivatives of 1,2-diaminoethane, (R)-1,2-diaminopropane, and (R,R)-1,2-diaminocyclohexane

Toshishige M. Suzuki, Shigeru Ohba, Shoichi Sato, Yoshihiko Saito, Kazuo Saito

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Abstract

Mixed-ligand cobalt(III) complexes have been prepared by the reaction of tris(acetylacetonato)cobalt(III) with an N,-N′-di-8-quinolyl-1,2-diaminoalkane (1,2-diaminoethane, (R)-1,2-diaminopropane, and (R,R)-1,2-diaminocyclohexane) in organic solvents. The isolated complexes have deprotonated secondary amino nitrogens. The parent complexes with neutral ligands were readily formed on addition of hydrogen chloride in organic solvents, but the crystals were isolated with difficulty. The absorption, CD, and 1H NMR spectra change rapidly and reversibly on protonation and deprotonation of the quadridentate ligand. The X-ray crystal structure analysis of [Co(acac)(R-dqpn′)]ClO4, which contains the deprotonated form of dqpn (dqpn = N,N′-di-8-quinolyl-1,2-diaminopropane), has been performed in order to clarify the detailed structure. Crystal data: CoClO6N4C26H26, a = 11.112 (2) Å, b = 13.299 (5) Å, c = 9.275 (4) Å, α = 106.06 (4)°, β = 88.72 (3)°, γ = 85.87 (3)°, space group P1, Z = 2, R = 5.7% for 4327 observed reflections. The two independent complex cations consist of the Δ- and Λ-isomers. The stereochemistry including geometrical and optical isomerism of both the protonated and deprotonated complexes is discussed on the basis of the crystal structure and spectroscopic data in solution. The quadridentate ligands seem to undergo rapid rearrangement on protonation and deprotonation of the complexes.

Original languageEnglish
Pages (from-to)2048-2054
Number of pages7
JournalInorganic Chemistry
Volume22
Issue number14
Publication statusPublished - 1983

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ethylenediamine
Cobalt
cobalt
Spectroscopy
Ligands
Derivatives
preparation
Deprotonation
ligands
Protonation
Organic solvents
spectroscopy
Crystal structure
Crystals
Stereochemistry
hydrogen chlorides
crystal structure
Hydrochloric Acid
stereochemistry
Isomers

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Preparation, structure, and spectroscopy of cobalt(III) complexes containing N,N′-di-8-quinolyl derivatives of 1,2-diaminoethane, (R)-1,2-diaminopropane, and (R,R)-1,2-diaminocyclohexane. / Suzuki, Toshishige M.; Ohba, Shigeru; Sato, Shoichi; Saito, Yoshihiko; Saito, Kazuo.

In: Inorganic Chemistry, Vol. 22, No. 14, 1983, p. 2048-2054.

Research output: Contribution to journalArticle

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title = "Preparation, structure, and spectroscopy of cobalt(III) complexes containing N,N′-di-8-quinolyl derivatives of 1,2-diaminoethane, (R)-1,2-diaminopropane, and (R,R)-1,2-diaminocyclohexane",
abstract = "Mixed-ligand cobalt(III) complexes have been prepared by the reaction of tris(acetylacetonato)cobalt(III) with an N,-N′-di-8-quinolyl-1,2-diaminoalkane (1,2-diaminoethane, (R)-1,2-diaminopropane, and (R,R)-1,2-diaminocyclohexane) in organic solvents. The isolated complexes have deprotonated secondary amino nitrogens. The parent complexes with neutral ligands were readily formed on addition of hydrogen chloride in organic solvents, but the crystals were isolated with difficulty. The absorption, CD, and 1H NMR spectra change rapidly and reversibly on protonation and deprotonation of the quadridentate ligand. The X-ray crystal structure analysis of [Co(acac)(R-dqpn′)]ClO4, which contains the deprotonated form of dqpn (dqpn = N,N′-di-8-quinolyl-1,2-diaminopropane), has been performed in order to clarify the detailed structure. Crystal data: CoClO6N4C26H26, a = 11.112 (2) {\AA}, b = 13.299 (5) {\AA}, c = 9.275 (4) {\AA}, α = 106.06 (4)°, β = 88.72 (3)°, γ = 85.87 (3)°, space group P1, Z = 2, R = 5.7{\%} for 4327 observed reflections. The two independent complex cations consist of the Δ- and Λ-isomers. The stereochemistry including geometrical and optical isomerism of both the protonated and deprotonated complexes is discussed on the basis of the crystal structure and spectroscopic data in solution. The quadridentate ligands seem to undergo rapid rearrangement on protonation and deprotonation of the complexes.",
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T1 - Preparation, structure, and spectroscopy of cobalt(III) complexes containing N,N′-di-8-quinolyl derivatives of 1,2-diaminoethane, (R)-1,2-diaminopropane, and (R,R)-1,2-diaminocyclohexane

AU - Suzuki, Toshishige M.

AU - Ohba, Shigeru

AU - Sato, Shoichi

AU - Saito, Yoshihiko

AU - Saito, Kazuo

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N2 - Mixed-ligand cobalt(III) complexes have been prepared by the reaction of tris(acetylacetonato)cobalt(III) with an N,-N′-di-8-quinolyl-1,2-diaminoalkane (1,2-diaminoethane, (R)-1,2-diaminopropane, and (R,R)-1,2-diaminocyclohexane) in organic solvents. The isolated complexes have deprotonated secondary amino nitrogens. The parent complexes with neutral ligands were readily formed on addition of hydrogen chloride in organic solvents, but the crystals were isolated with difficulty. The absorption, CD, and 1H NMR spectra change rapidly and reversibly on protonation and deprotonation of the quadridentate ligand. The X-ray crystal structure analysis of [Co(acac)(R-dqpn′)]ClO4, which contains the deprotonated form of dqpn (dqpn = N,N′-di-8-quinolyl-1,2-diaminopropane), has been performed in order to clarify the detailed structure. Crystal data: CoClO6N4C26H26, a = 11.112 (2) Å, b = 13.299 (5) Å, c = 9.275 (4) Å, α = 106.06 (4)°, β = 88.72 (3)°, γ = 85.87 (3)°, space group P1, Z = 2, R = 5.7% for 4327 observed reflections. The two independent complex cations consist of the Δ- and Λ-isomers. The stereochemistry including geometrical and optical isomerism of both the protonated and deprotonated complexes is discussed on the basis of the crystal structure and spectroscopic data in solution. The quadridentate ligands seem to undergo rapid rearrangement on protonation and deprotonation of the complexes.

AB - Mixed-ligand cobalt(III) complexes have been prepared by the reaction of tris(acetylacetonato)cobalt(III) with an N,-N′-di-8-quinolyl-1,2-diaminoalkane (1,2-diaminoethane, (R)-1,2-diaminopropane, and (R,R)-1,2-diaminocyclohexane) in organic solvents. The isolated complexes have deprotonated secondary amino nitrogens. The parent complexes with neutral ligands were readily formed on addition of hydrogen chloride in organic solvents, but the crystals were isolated with difficulty. The absorption, CD, and 1H NMR spectra change rapidly and reversibly on protonation and deprotonation of the quadridentate ligand. The X-ray crystal structure analysis of [Co(acac)(R-dqpn′)]ClO4, which contains the deprotonated form of dqpn (dqpn = N,N′-di-8-quinolyl-1,2-diaminopropane), has been performed in order to clarify the detailed structure. Crystal data: CoClO6N4C26H26, a = 11.112 (2) Å, b = 13.299 (5) Å, c = 9.275 (4) Å, α = 106.06 (4)°, β = 88.72 (3)°, γ = 85.87 (3)°, space group P1, Z = 2, R = 5.7% for 4327 observed reflections. The two independent complex cations consist of the Δ- and Λ-isomers. The stereochemistry including geometrical and optical isomerism of both the protonated and deprotonated complexes is discussed on the basis of the crystal structure and spectroscopic data in solution. The quadridentate ligands seem to undergo rapid rearrangement on protonation and deprotonation of the complexes.

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