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
DOIs
Publication statusPublished - Jan 1 1998
Externally publishedYes

Keywords

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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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