Preparation, crystal structures, and spectroscopic and redox properties of nickel(II) complexes containing phosphane-(amine or quinoline)-type hybrid ligands and a nickel(I) complex bearing 8-(diphenylphosphanyl)quinoliney

Akira Hashimoto, Hiroshi Yamaguchi, Takayoshi Suzuki, Kazuo Kashiwabara, Masaaki Kojima, Hideo D. Takagi

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Abstract

Nickel(II) complexes containing P-N-type bidentate hybrid ligands of 2-aminoethylphosphanes (RR'Pea; RR' = Ph2 or MePh) or 8-quinolylphosphanes (RR'Pqn), namely [Ni(P-N)2](BF4) 2 [P-N = Ph2Pea (1), MePhPea (2), Ph2Pqn (3), or MePhPqn (4)] have been prepared, and their structural, spectroscopic, and electrochemical properties determined. The crystal structure analysis indicates that: the 2-amlnoethylphosphane complexes (1 and 2) have a square-planar coordination geometry around the NiII center with a cis(P,P) configuration, whereas the 8-quinolylphosphane complexes (3 and 4) exhibit a severe tetrahedral distortion because of the steric repulsion between the ortho-H atoms in the mutually cis-positioned quinolyl rings, Complexes 1 and 2 maintain their diamagnetic square-planar four-coordinate structure on acetonitrile solution, whereas complexes 3 and 4 show paramagnetic behavior. Spectroscopic and electrochemical measurements suggest that the ligand-field strengths of these four PN-type ligands increase in the order Ph2Pqn (3) <MePhPqn (4) <Ph2Pea (1) <MePhPea (2). The Ph 2Pqn complex 3 is readily reduced by Zn powder to afford the corresponding nickel(I) complex [Ni(Ph2Pqn)2]BF 4 (5), The crystal structure of complex 5 reveals that the Ni I ion adopts a distorted tetrahedral coordination geometry with slightly longer (≈ 0.05 Å) Ni-P and. Ni-N bond lengths than those in the corresponding NiII complex 3.

Original languageEnglish
Pages (from-to)39-47
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number1
DOIs
Publication statusPublished - 2010

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phosphine
Bearings (structural)
Nickel
Amines
Crystal structure
Ligands
Geometry
Bond length
Electrochemical properties
Powders
Ions
Atoms
Oxidation-Reduction
quinoline

Keywords

  • Ligand effects
  • N,p ligands
  • Nickel
  • Phosphane ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{28c6ac7ea7294a1d8846db67f4313bf1,
title = "Preparation, crystal structures, and spectroscopic and redox properties of nickel(II) complexes containing phosphane-(amine or quinoline)-type hybrid ligands and a nickel(I) complex bearing 8-(diphenylphosphanyl)quinoliney",
abstract = "Nickel(II) complexes containing P-N-type bidentate hybrid ligands of 2-aminoethylphosphanes (RR'Pea; RR' = Ph2 or MePh) or 8-quinolylphosphanes (RR'Pqn), namely [Ni(P-N)2](BF4) 2 [P-N = Ph2Pea (1), MePhPea (2), Ph2Pqn (3), or MePhPqn (4)] have been prepared, and their structural, spectroscopic, and electrochemical properties determined. The crystal structure analysis indicates that: the 2-amlnoethylphosphane complexes (1 and 2) have a square-planar coordination geometry around the NiII center with a cis(P,P) configuration, whereas the 8-quinolylphosphane complexes (3 and 4) exhibit a severe tetrahedral distortion because of the steric repulsion between the ortho-H atoms in the mutually cis-positioned quinolyl rings, Complexes 1 and 2 maintain their diamagnetic square-planar four-coordinate structure on acetonitrile solution, whereas complexes 3 and 4 show paramagnetic behavior. Spectroscopic and electrochemical measurements suggest that the ligand-field strengths of these four PN-type ligands increase in the order Ph2Pqn (3) <MePhPqn (4) <Ph2Pea (1) <MePhPea (2). The Ph 2Pqn complex 3 is readily reduced by Zn powder to afford the corresponding nickel(I) complex [Ni(Ph2Pqn)2]BF 4 (5), The crystal structure of complex 5 reveals that the Ni I ion adopts a distorted tetrahedral coordination geometry with slightly longer (≈ 0.05 {\AA}) Ni-P and. Ni-N bond lengths than those in the corresponding NiII complex 3.",
keywords = "Ligand effects, N,p ligands, Nickel, Phosphane ligands",
author = "Akira Hashimoto and Hiroshi Yamaguchi and Takayoshi Suzuki and Kazuo Kashiwabara and Masaaki Kojima and Takagi, {Hideo D.}",
year = "2010",
doi = "10.1002/ejic.200900767",
language = "English",
pages = "39--47",
journal = "Chemische Berichte",
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TY - JOUR

T1 - Preparation, crystal structures, and spectroscopic and redox properties of nickel(II) complexes containing phosphane-(amine or quinoline)-type hybrid ligands and a nickel(I) complex bearing 8-(diphenylphosphanyl)quinoliney

AU - Hashimoto, Akira

AU - Yamaguchi, Hiroshi

AU - Suzuki, Takayoshi

AU - Kashiwabara, Kazuo

AU - Kojima, Masaaki

AU - Takagi, Hideo D.

PY - 2010

Y1 - 2010

N2 - Nickel(II) complexes containing P-N-type bidentate hybrid ligands of 2-aminoethylphosphanes (RR'Pea; RR' = Ph2 or MePh) or 8-quinolylphosphanes (RR'Pqn), namely [Ni(P-N)2](BF4) 2 [P-N = Ph2Pea (1), MePhPea (2), Ph2Pqn (3), or MePhPqn (4)] have been prepared, and their structural, spectroscopic, and electrochemical properties determined. The crystal structure analysis indicates that: the 2-amlnoethylphosphane complexes (1 and 2) have a square-planar coordination geometry around the NiII center with a cis(P,P) configuration, whereas the 8-quinolylphosphane complexes (3 and 4) exhibit a severe tetrahedral distortion because of the steric repulsion between the ortho-H atoms in the mutually cis-positioned quinolyl rings, Complexes 1 and 2 maintain their diamagnetic square-planar four-coordinate structure on acetonitrile solution, whereas complexes 3 and 4 show paramagnetic behavior. Spectroscopic and electrochemical measurements suggest that the ligand-field strengths of these four PN-type ligands increase in the order Ph2Pqn (3) <MePhPqn (4) <Ph2Pea (1) <MePhPea (2). The Ph 2Pqn complex 3 is readily reduced by Zn powder to afford the corresponding nickel(I) complex [Ni(Ph2Pqn)2]BF 4 (5), The crystal structure of complex 5 reveals that the Ni I ion adopts a distorted tetrahedral coordination geometry with slightly longer (≈ 0.05 Å) Ni-P and. Ni-N bond lengths than those in the corresponding NiII complex 3.

AB - Nickel(II) complexes containing P-N-type bidentate hybrid ligands of 2-aminoethylphosphanes (RR'Pea; RR' = Ph2 or MePh) or 8-quinolylphosphanes (RR'Pqn), namely [Ni(P-N)2](BF4) 2 [P-N = Ph2Pea (1), MePhPea (2), Ph2Pqn (3), or MePhPqn (4)] have been prepared, and their structural, spectroscopic, and electrochemical properties determined. The crystal structure analysis indicates that: the 2-amlnoethylphosphane complexes (1 and 2) have a square-planar coordination geometry around the NiII center with a cis(P,P) configuration, whereas the 8-quinolylphosphane complexes (3 and 4) exhibit a severe tetrahedral distortion because of the steric repulsion between the ortho-H atoms in the mutually cis-positioned quinolyl rings, Complexes 1 and 2 maintain their diamagnetic square-planar four-coordinate structure on acetonitrile solution, whereas complexes 3 and 4 show paramagnetic behavior. Spectroscopic and electrochemical measurements suggest that the ligand-field strengths of these four PN-type ligands increase in the order Ph2Pqn (3) <MePhPqn (4) <Ph2Pea (1) <MePhPea (2). The Ph 2Pqn complex 3 is readily reduced by Zn powder to afford the corresponding nickel(I) complex [Ni(Ph2Pqn)2]BF 4 (5), The crystal structure of complex 5 reveals that the Ni I ion adopts a distorted tetrahedral coordination geometry with slightly longer (≈ 0.05 Å) Ni-P and. Ni-N bond lengths than those in the corresponding NiII complex 3.

KW - Ligand effects

KW - N,p ligands

KW - Nickel

KW - Phosphane ligands

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U2 - 10.1002/ejic.200900767

DO - 10.1002/ejic.200900767

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