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 language | English |
|---|---|
| Pages (from-to) | 1943-1952 |
| Number of pages | 10 |
| Journal | Polyhedron |
| Volume | 17 |
| Issue number | 11-12 |
| Publication status | Published - 1998 |
| Externally published | Yes |
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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 journal › Article
}
TY - JOUR
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
AU - Fukushima, Yuuji
AU - Mimura, Masaaki
AU - Hirohata, Masaaki
AU - Matsumoto, Naohide
AU - Kai, Fumiaki
PY - 1998
Y1 - 1998
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.
KW - Crystal structure
KW - Equatorially elongated octahedral copper(II) complex
KW - ESR spectra
KW - Hexadentate thioether ligand
KW - Redox potential
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M3 - Article
AN - SCOPUS:0000785588
VL - 17
SP - 1943
EP - 1952
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
IS - 11-12
ER -