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Related Experiment Videos

Pentacoordinate oxyphosphorane intermediate always exists in aqueous solution.

A Yliniemela1, T Uchimaru, K Tanabe

  • 1Technical Research Centre, Chemical Laboratory, Finland.

Nucleic Acids Symposium Series
|January 1, 1992
PubMed
Summary
This summary is machine-generated.

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Dianionic pentacoordinate oxyphosphoranes generally lack a stable intermediate. However, solvation with water can stabilize these intermediates, supporting their role in phosphoryl transfer reactions across different pH conditions.

Area of Science:

  • Computational chemistry
  • Inorganic chemistry
  • Biochemistry

Background:

  • Phosphoryl transfer reactions are crucial in biological systems.
  • The mechanism of phosphoryl transfer, particularly the role of intermediates, is still debated.
  • Pentacoordinate oxyphosphoranes are proposed intermediates in these reactions.

Purpose of the Study:

  • To investigate the kinetic stability of dianionic pentacoordinate oxyphosphoranes using computational methods.
  • To determine if these species can act as kinetically meaningful intermediates in phosphoryl transfer.
  • To explore the influence of solvation on the stability of these intermediates.

Main Methods:

  • Gas-phase ab initio calculations were employed.
  • The simplest oxyphosphorane, PO5H3(2-), was studied.

Related Experiment Videos

  • The effect of solvation by six water molecules was simulated.

    • Main Results:

    • Gas-phase calculations suggest dianionic pentacoordinate oxyphosphoranes are not kinetically stable intermediates.
    • The simplest oxyphosphorane, PO5H3(2-), showed the least tendency for a pentacoordinate intermediate.
    • Solvation with six water molecules enabled the formation of a pentacoordinate intermediate for PO5H3(2-).

    Conclusions:

    • The findings challenge the universal role of pentacoordinate intermediates in all conditions.
    • Solvation is critical for the formation and potential stability of these intermediates.
    • These results support the hypothesis that phosphoryl transfer reactions can proceed via pentacoordinate intermediates in both acidic and basic media.