Metal Cation Micelle Mediated Hydrolysis of Phosphonic Acid Esters

p-Nitrophenyl methylphosphonate (PNPMP, 3) and p-nitrophenyl phenylphosphonate (PNPPP, 4) are rapidly hydrolyzed in acidic solutions (pH 3.5−6.0) at 37 °C by excess Zr4+, Ce4+, or Th4+ cations. Brij-35 micelles are employed in the Ce4+ and Th4+ cases. Second-order rate constants (M-1 s-1) with PNPMP...

Full description

Saved in:
Bibliographic Details
Published in:Langmuir 1999-01, Vol.15 (1), p.107-110
Main Authors: Moss, Robert A, Ragunathan, Kaliappa G
Format: Article
Language:English
Subjects:
Catalysis
Catalytic reactions
Chemistry
Colloidal state and disperse state
Exact sciences and technology
General and physical chemistry
Micelles. Thin films
Organic chemistry
Preparations and properties
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:p-Nitrophenyl methylphosphonate (PNPMP, 3) and p-nitrophenyl phenylphosphonate (PNPPP, 4) are rapidly hydrolyzed in acidic solutions (pH 3.5−6.0) at 37 °C by excess Zr4+, Ce4+, or Th4+ cations. Brij-35 micelles are employed in the Ce4+ and Th4+ cases. Second-order rate constants (M-1 s-1) with PNPMP are 115 (Zr4+), 53.9 (Ce4+), and 16.9 (Th4+), while for PNPPP they are, respectively, 76.8, 16.1, and 13.1. Relative to water (k 2 = 3.6 × 10-11 M-1 s-1 at 30 °C, pH 7.6), kinetic advantages with Zr4+ or Ce4+ exceed 1012.
ISSN:0743-7463
1520-5827
DOI:10.1021/la981110a