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Methyl methylphenylphosphinate, MePh(MeO)PO complexes of the first row transition metals

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Summary

Methyl methylphenylphosphinate (L) complexes with 3d metal perchlorates were synthesized by interaction of L and metal salt solutions in triethyl orthoformate (6∶1 molar ratio) and characterized by means of spectral, magnetic and conductance studies. In most cases (Mn+ = Cr3+, Mn2+, Co2+, Ni2+, Cu2+ or Zn2+), complexes involving 4∶1 L: metal ratios, similar to those obtained with bulky triorganophosphine oxides and neutral phosphonate or phosphate esters, were formed. These complexes contain exclusively terminal L groups and were characterized as monomeric of the types [CrL4(OClO3)2](ClO4), [ML4(OH2)](ClO4)2 (M = Mn or Ni), [ML4(OClO3)](ClO4) (M = Co or Zn) and [CuL4](ClO4)2. In contrast, Fe2+ and Fe3+ perchlorates formed, rather unexpectedly, complexes involving 2∶1 L: Fe ratios. These compounds appear to be binuclear and of the type [(O3ClO)(H2O)2LFeL2FeL(OH2)2(OClO3)](ClO4)n (n=2 for Fe2+; n=4 for Fe3+), containing both terminal and bridging coordinated L ligands. The bridging L groups in the iron complexes seem to be exclusively coordinated through the P=O oxygen, which acts as a bridging group between two adjacent Fe2+ or Fe3+ions, rather than functioning as bidentate bridging O,O-ligands, with both the P=O and methoxy oxygens involved in coordination. Spectral evidence suggests that L is a weaker ligand than triorganophosphine oxides and a stronger ligand than neutral phosphonate and phosphate esters, as anticipated.

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Authors and Affiliations

  1. Department of Chemistry and Physics, Beaver College, 19038, Glenside, Pa., USA

    Chester M. Mikulski & Joseph Unruh

  2. Department of Chemistry, Drexel University, 19104, Philadelphia, Pa., USA

    Louis L. Pytlewski

  3. Amoco Chemicals Corporation, 60540, Naperville, Il., USA

    Nicholas M. Karayannis

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  1. Chester M. Mikulski
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  4. Nicholas M. Karayannis
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Mikulski, C.M., Unruh, J., Pytlewski, L.L. et al. Methyl methylphenylphosphinate, MePh(MeO)PO complexes of the first row transition metals. Transition Met Chem 4, 98–103 (1979). https://doi.org/10.1007/BF00618833

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