Effect of divalent metal ions on the intramolecular nucleophilic catalysis of phosphate diester hydrolysis

James J. Steffens, Eric J. Sampson, Iris J. Siewers, Stephen Benkovic

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Abstract

Recent investigations1, 2 have demonstrated that remarkable rate enhancements may be obtained in the hydrolysis of phosphate diesters by suitably positioning nucleophilic groups within the reacting molecule. Moreover, these reactions are thought to proceed via metastable pentacovalent intermediates owing to the magnitude of the rate enhancements (104-108), high sensitivity to changes in leaving group pKa (β = — 1.2), and the marked preference (>90%) for exocyclic ligand loss. We wish to report that the rates for these intramolecular systems are significantly increased by biologically important divalent metal ions and include an important example of Mg2+ ion catalysis. The data furthermore suggest that a major fraction of the metal ion catalysis may arise from a unique stabilizing interaction between the metal ion and the intermediate pentacovalent species.

Original languageEnglish (US)
Pages (from-to)936-938
Number of pages3
JournalJournal of the American Chemical Society
Volume95
Issue number3
DOIs
Publication statusPublished - Feb 1 1973

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All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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