Syntheses, Crystal Structures and Ligand Field Properties of Iron(II) Complexes with PNP Ligands: Origin of Large Ligand Field by a Phosphorous Donor Atom

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-D4h 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.