Altered mechanisms of reactions of phosphate esters bridging a dinuclear metal center

J Am Chem Soc. 2004 Sep 29;126(38):11864-9. doi: 10.1021/ja047110g.

Abstract

Kinetic isotope effects in the nucleophile and leaving group were obtained for the reaction of p-nitrophenyl phosphate monoester coordinated to a dinuclear Co(III) complex. The metal complex of the p-nitrophenyl phosphate monoester was found to hydrolyze by a single-step concerted mechanism, with significant nucleophilic participation in the transition state. By contrast, the hydrolysis of uncomplexed p-nitrophenyl phosphate occurs by a very loose transition state with little bond formation to the nucleophile. Previously, the metal complex of the diester methyl-p-nitrophenyl phosphate was found to hydrolyze via a two-step addition-elimination mechanism, in contrast to the concerted hydrolysis mechanism followed by uncomplexed diesters with the p-nitrophenolate leaving group. These results show that coordination to a metal complex can significantly alter the mechanism of phosphoryl transfer.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Cobalt / chemistry*
  • Hydrolysis
  • Kinetics
  • Nitrophenols / chemistry*
  • Organometallic Compounds / chemistry
  • Organophosphates / chemistry*
  • Organophosphorus Compounds / chemistry*
  • Oxygen Isotopes
  • Thermodynamics

Substances

  • Nitrophenols
  • Organometallic Compounds
  • Organophosphates
  • Organophosphorus Compounds
  • Oxygen Isotopes
  • nitrophenylphosphate
  • Cobalt