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)<inf>2</inf>](PF<inf>6</inf>)<inf>2</inf>·CH<inf>3</inf>NO<inf>2</inf> and mer-[Fe(PpyP)<inf>2</inf>](CF<inf>3</inf>SO<inf>3</inf>)<inf>2</inf>, 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 <inf>4h</inf> 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 Ph<inf>2</inf>P-donor sites and by the axial 2,6-disubstituted pyridine donor sites is ca. 13,200 cm<sup>-1</sup>. A significantly reduced inter-electronic repulsion parameter (425 cm<sup>-1</sup> for both PNP and PpyP complexes) from the value of the free ion (1,060 cm<sup>-1</sup>) 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 - 2014 Oct 21

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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

    AU - Suzuki, Takayoshi

    AU - Takagi, Hideo D.

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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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