Synthesis, crystal structures and electrochemical properties of CuII and NiII complexes with hexadentate ligands containing thioether-amido-pyridyl donor set

Yukinari Sunatsuki, Takehisa Matsumoto, Yuuji Fukushima, Masaaki Mimura, Masaaki Hirohata, Naohide Matsumoto, Fumiaki Kai

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Novel two acyclic hexadentate ligands, 1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,4-dithiobutane (H2bpctb) and 1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,5-dithiopentane (H2bpctp), containing thioether functions were synthesized and their copper(II) and nickel(II) complexes [(Cu(bpctb)], 1; [Cu(bpctp)], 2; [Ni(bpctb)], 3 and [Ni(bpctp)], 4) were prepared. The structures of 1-4 were determined by X-ray crystallography. The coordination geometries of 3 and 4 are octahedral with two amido and two pyridyl nitrogen atoms and two thioether sulfur atoms of hexadentate ligand. However, the coordination geometry of 2 is a flattened tetrahedron combining two amido nitrogen atoms and two pyridyl nitrogen atoms of hexadentate ligand without thioether coordination. X-ray crystallography and ESR spectroscopic studies revealed that the coordination geometry of 1 is an uncommon equatorially elongated octahedron in solid state. However, this coordination geometry changes to an axially elongated one in solution. The copper(II/I) redox processes for 1 and 2 are around - 1.2 V and the nickel(II/III) processes for 3 and 4 at around 0.3 V vs ferrocene/ferrocenium couple were observed in DMSO.

Original languageEnglish
Pages (from-to)1943-1952
Number of pages10
JournalPolyhedron
Volume17
Issue number11-12
Publication statusPublished - 1998
Externally publishedYes

Fingerprint

Sulfides
Electrochemical properties
Nitrogen
Crystal structure
X Ray Crystallography
Ligands
Nickel
Atoms
ligands
crystal structure
Geometry
Copper
X ray crystallography
nitrogen atoms
synthesis
Pyridine
geometry
crystallography
Dimethyl Sulfoxide
pyridines

Keywords

  • Crystal structure
  • Equatorially elongated octahedral copper(II) complex
  • ESR spectra
  • Hexadentate thioether ligand
  • Redox potential

ASJC Scopus subject areas

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

Cite this

Synthesis, crystal structures and electrochemical properties of CuII and NiII complexes with hexadentate ligands containing thioether-amido-pyridyl donor set. / Sunatsuki, Yukinari; Matsumoto, Takehisa; Fukushima, Yuuji; Mimura, Masaaki; Hirohata, Masaaki; Matsumoto, Naohide; Kai, Fumiaki.

In: Polyhedron, Vol. 17, No. 11-12, 1998, p. 1943-1952.

Research output: Contribution to journalArticle

Sunatsuki, Y, Matsumoto, T, Fukushima, Y, Mimura, M, Hirohata, M, Matsumoto, N & Kai, F 1998, 'Synthesis, crystal structures and electrochemical properties of CuII and NiII complexes with hexadentate ligands containing thioether-amido-pyridyl donor set', Polyhedron, vol. 17, no. 11-12, pp. 1943-1952.
Sunatsuki, Yukinari ; Matsumoto, Takehisa ; Fukushima, Yuuji ; Mimura, Masaaki ; Hirohata, Masaaki ; Matsumoto, Naohide ; Kai, Fumiaki. / Synthesis, crystal structures and electrochemical properties of CuII and NiII complexes with hexadentate ligands containing thioether-amido-pyridyl donor set. In: Polyhedron. 1998 ; Vol. 17, No. 11-12. pp. 1943-1952.
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T1 - Synthesis, crystal structures and electrochemical properties of CuII and NiII complexes with hexadentate ligands containing thioether-amido-pyridyl donor set

AU - Sunatsuki, Yukinari

AU - Matsumoto, Takehisa

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AU - Mimura, Masaaki

AU - Hirohata, Masaaki

AU - Matsumoto, Naohide

AU - Kai, Fumiaki

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N2 - Novel two acyclic hexadentate ligands, 1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,4-dithiobutane (H2bpctb) and 1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,5-dithiopentane (H2bpctp), containing thioether functions were synthesized and their copper(II) and nickel(II) complexes [(Cu(bpctb)], 1; [Cu(bpctp)], 2; [Ni(bpctb)], 3 and [Ni(bpctp)], 4) were prepared. The structures of 1-4 were determined by X-ray crystallography. The coordination geometries of 3 and 4 are octahedral with two amido and two pyridyl nitrogen atoms and two thioether sulfur atoms of hexadentate ligand. However, the coordination geometry of 2 is a flattened tetrahedron combining two amido nitrogen atoms and two pyridyl nitrogen atoms of hexadentate ligand without thioether coordination. X-ray crystallography and ESR spectroscopic studies revealed that the coordination geometry of 1 is an uncommon equatorially elongated octahedron in solid state. However, this coordination geometry changes to an axially elongated one in solution. The copper(II/I) redox processes for 1 and 2 are around - 1.2 V and the nickel(II/III) processes for 3 and 4 at around 0.3 V vs ferrocene/ferrocenium couple were observed in DMSO.

AB - Novel two acyclic hexadentate ligands, 1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,4-dithiobutane (H2bpctb) and 1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,5-dithiopentane (H2bpctp), containing thioether functions were synthesized and their copper(II) and nickel(II) complexes [(Cu(bpctb)], 1; [Cu(bpctp)], 2; [Ni(bpctb)], 3 and [Ni(bpctp)], 4) were prepared. The structures of 1-4 were determined by X-ray crystallography. The coordination geometries of 3 and 4 are octahedral with two amido and two pyridyl nitrogen atoms and two thioether sulfur atoms of hexadentate ligand. However, the coordination geometry of 2 is a flattened tetrahedron combining two amido nitrogen atoms and two pyridyl nitrogen atoms of hexadentate ligand without thioether coordination. X-ray crystallography and ESR spectroscopic studies revealed that the coordination geometry of 1 is an uncommon equatorially elongated octahedron in solid state. However, this coordination geometry changes to an axially elongated one in solution. The copper(II/I) redox processes for 1 and 2 are around - 1.2 V and the nickel(II/III) processes for 3 and 4 at around 0.3 V vs ferrocene/ferrocenium couple were observed in DMSO.

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