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Sterically encumbered acyclic diphosphazanes: synthesis, conformations and coordination behavior.

Ganesan Prabusankar1, Nallasamy Palanisami, Ramaswamy Murugavel

  • 1Department of Chemistry, Indian Institute of Technology-Bombay, Powai, Mumbai, 400 076, India.

Dalton Transactions (Cambridge, England : 2003)
|April 21, 2006
PubMed
Summary

Sterically encumbered diphosphazanes were synthesized from lambda3-diphosphazane and substituted phenols. Structural studies revealed bulky groups on phosphorus and nitrogen align, maintaining trigonal planar geometry for the central nitrogen.

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Area of Science:

  • Organophosphorus Chemistry
  • Coordination Chemistry
  • Crystallography

Background:

  • Diphosphazanes are versatile phosphorus-nitrogen compounds.
  • Steric hindrance plays a crucial role in chemical reactivity and structure.
  • Metal complexes of organophosphorus ligands offer unique catalytic and electronic properties.

Purpose of the Study:

  • To synthesize novel sterically encumbered diphosphazanes.
  • To investigate the impact of bulky phenolic substituents on diphosphazane formation.
  • To explore the coordination chemistry of these diphosphazanes with transition metals.

Main Methods:

  • Reaction of lambda3-diphosphazane with sodium salts of substituted phenols.
  • Characterization using elemental analysis, mass spectrometry (EI-MS), infrared (IR) spectroscopy, and multinuclear nuclear magnetic resonance (NMR) spectroscopy (1H and 31P).

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  • X-ray diffraction studies for solid-state structure determination of diphosphazanes and the molybdenum complex.

    • Main Results:

    • Synthesis of sterically encumbered diphosphazanes [EtN{P(OR)2}2] (1-3) and a monosubstituted product [EtN{PCl(OR)}2] (4) using bulky phenols.
    • Formation of a molybdenum complex cis-[(EtN{P(OC6H3Me2-2,6)2}2)Mo(CO)4] (5) from diphosphazane 2.
    • X-ray studies confirmed bulky groups on phosphorus and nitrogen are oriented on the same side of the P-N-P skeleton, exhibiting local C2v symmetry.
    • The central nitrogen atom consistently displays nearly trigonal planar geometry.

    Conclusions:

    • Steric bulk of phenolic substituents dictates the substitution pattern in diphosphazane synthesis.
    • The synthesized diphosphazanes can act as ligands in transition metal complexes.
    • The observed structural features highlight the influence of steric effects on molecular geometry and symmetry in organophosphorus compounds.