Syntheses, crystal structures and ligand field properties of Iron(II) complexes with PNP ligands

Origin of large ligand field by a phosphorous donor atom

Takuya Mabe, Hiroshi Yamaguchi, Masayuki Fujiki, Kyoko Noda, Koji Ishihara, Masahiko Inamo, Refat Moustafa Hassan, Satoshi Iwatsuki, Takayoshi Suzuki, Hideo D. Takagi

Research output: Contribution to journalArticle

Abstract

New iron(II) complexes were synthesized with two tridentate hybrid ligands having phosphorous and nitrogen donor sites, in order to quantitatively estimate the difference of the ligand-field strengths of phosphorous and nitrogen donor sites in cationic metal complexes. Iron(II) complexes with bis(dimethylphosphinoethyl)amine (PNP) and 2,6-bis(diphenylphosphinomethyl)pyridine (PpyP) ligands crystallized as un-symmetric facial-[Fe(PNP)2](PF6)2·CH3NO2 and mer-[Fe(PpyP)2](CF3SO3)2, respectively, as expected from the steric congestion and from the tendency to avoid the mutual trans influence between two phosphorous donor sites. Both complexes are in the low-spin electronic state up to 400 K. The pseudo-D 4h coordination geometry of the PpyP complex made it possible to separate axial (2 × N) and equatorial (4 × P) contributions to the overall ligand-field by means of a spectrometric method: the difference in the ligand-field strengths by the equatorial Ph2P-donor sites and by the axial 2,6-disubstituted pyridine donor sites is ca. 13,200 cm-1. A significantly reduced inter-electronic repulsion parameter (425 cm-1 for both PNP and PpyP complexes) from the value of the free ion (1,060 cm-1) indicates covalent interaction between the Fe(II) and P atoms even in these cationic metal complexes. It is shown that the degree of covalency as well as the coordination bond strengths between various metal ions and phosphorous/nitrogen donor atoms is successfully explained by the relative energy levels of interacting atomic orbitals calculated on the basis of the Thomas-Fermi-Dirac potential.

Original languageEnglish
Pages (from-to)1574-1587
Number of pages14
JournalJournal of Solution Chemistry
Volume43
Issue number9-10
DOIs
Publication statusPublished - Oct 21 2014

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pyridines
Iron
Crystal structure
Ligands
iron
Atoms
ligands
crystal structure
synthesis
Nitrogen
Coordination Complexes
atoms
nitrogen
field strength
Ions
congestion
Electronic states
electronics
metals
Electron energy levels

Keywords

  • 2, 6-Bis(diphenylphosphinomethyl)pyridine (PpyP)
  • Bis(dimethylphosphinoethyl)amine (PNP)
  • Iron(II) complexes
  • Ligand field

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Biochemistry
  • Biophysics
  • Molecular Biology

Cite this

Syntheses, crystal structures and ligand field properties of Iron(II) complexes with PNP ligands : Origin of large ligand field by a phosphorous donor atom. / Mabe, Takuya; Yamaguchi, Hiroshi; Fujiki, Masayuki; Noda, Kyoko; Ishihara, Koji; Inamo, Masahiko; Hassan, Refat Moustafa; Iwatsuki, Satoshi; Suzuki, Takayoshi; Takagi, Hideo D.

In: Journal of Solution Chemistry, Vol. 43, No. 9-10, 21.10.2014, p. 1574-1587.

Research output: Contribution to journalArticle

Mabe, Takuya ; Yamaguchi, Hiroshi ; Fujiki, Masayuki ; Noda, Kyoko ; Ishihara, Koji ; Inamo, Masahiko ; Hassan, Refat Moustafa ; Iwatsuki, Satoshi ; Suzuki, Takayoshi ; Takagi, Hideo D. / Syntheses, crystal structures and ligand field properties of Iron(II) complexes with PNP ligands : Origin of large ligand field by a phosphorous donor atom. In: Journal of Solution Chemistry. 2014 ; Vol. 43, No. 9-10. pp. 1574-1587.
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abstract = "New iron(II) complexes were synthesized with two tridentate hybrid ligands having phosphorous and nitrogen donor sites, in order to quantitatively estimate the difference of the ligand-field strengths of phosphorous and nitrogen donor sites in cationic metal complexes. Iron(II) complexes with bis(dimethylphosphinoethyl)amine (PNP) and 2,6-bis(diphenylphosphinomethyl)pyridine (PpyP) ligands crystallized as un-symmetric facial-[Fe(PNP)2](PF6)2·CH3NO2 and mer-[Fe(PpyP)2](CF3SO3)2, respectively, as expected from the steric congestion and from the tendency to avoid the mutual trans influence between two phosphorous donor sites. Both complexes are in the low-spin electronic state up to 400 K. The pseudo-D 4h coordination geometry of the PpyP complex made it possible to separate axial (2 × N) and equatorial (4 × P) contributions to the overall ligand-field by means of a spectrometric method: the difference in the ligand-field strengths by the equatorial Ph2P-donor sites and by the axial 2,6-disubstituted pyridine donor sites is ca. 13,200 cm-1. A significantly reduced inter-electronic repulsion parameter (425 cm-1 for both PNP and PpyP complexes) from the value of the free ion (1,060 cm-1) indicates covalent interaction between the Fe(II) and P atoms even in these cationic metal complexes. It is shown that the degree of covalency as well as the coordination bond strengths between various metal ions and phosphorous/nitrogen donor atoms is successfully explained by the relative energy levels of interacting atomic orbitals calculated on the basis of the Thomas-Fermi-Dirac potential.",
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AU - Yamaguchi, Hiroshi

AU - Fujiki, Masayuki

AU - Noda, Kyoko

AU - Ishihara, Koji

AU - Inamo, Masahiko

AU - Hassan, Refat Moustafa

AU - Iwatsuki, Satoshi

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AB - New iron(II) complexes were synthesized with two tridentate hybrid ligands having phosphorous and nitrogen donor sites, in order to quantitatively estimate the difference of the ligand-field strengths of phosphorous and nitrogen donor sites in cationic metal complexes. Iron(II) complexes with bis(dimethylphosphinoethyl)amine (PNP) and 2,6-bis(diphenylphosphinomethyl)pyridine (PpyP) ligands crystallized as un-symmetric facial-[Fe(PNP)2](PF6)2·CH3NO2 and mer-[Fe(PpyP)2](CF3SO3)2, respectively, as expected from the steric congestion and from the tendency to avoid the mutual trans influence between two phosphorous donor sites. Both complexes are in the low-spin electronic state up to 400 K. The pseudo-D 4h coordination geometry of the PpyP complex made it possible to separate axial (2 × N) and equatorial (4 × P) contributions to the overall ligand-field by means of a spectrometric method: the difference in the ligand-field strengths by the equatorial Ph2P-donor sites and by the axial 2,6-disubstituted pyridine donor sites is ca. 13,200 cm-1. A significantly reduced inter-electronic repulsion parameter (425 cm-1 for both PNP and PpyP complexes) from the value of the free ion (1,060 cm-1) indicates covalent interaction between the Fe(II) and P atoms even in these cationic metal complexes. It is shown that the degree of covalency as well as the coordination bond strengths between various metal ions and phosphorous/nitrogen donor atoms is successfully explained by the relative energy levels of interacting atomic orbitals calculated on the basis of the Thomas-Fermi-Dirac potential.

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