The influence of the boat-to-chair conversion on the demetallation of the nickel(II) complex of an open-chain tetramine containing a piperazine fragment

Dalton Trans. 2004 Feb 21:(4):653-8. doi: 10.1039/b312980b. Epub 2004 Jan 21.

Abstract

The nickel(II) complex with an open chain tetramine containing a piperazine fragment (1) displays an unusual resistance to demetallation in acidic solution and exhibits a lifetime of about five minutes in a solution 0.1 M in HClO4 and 7.0 M in NaClO4. Sluggishness with respect to the demetallation is ascribed to the occurrence of the boat-to-chair conformational conversion of the piperazine fragment, which implies the passage through the highly energetic half-boat transition state. The use of a high concentration of the inert electrolyte induces a 'salting out' effect on both thermodynamics (stability of metal complexes is enhanced) and kinetics (resistance to demetallation is increased).

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bridged-Ring Compounds / chemistry*
  • Crystallography, X-Ray
  • Hydrogen-Ion Concentration
  • Kinetics
  • Models, Chemical
  • Models, Molecular
  • Molecular Conformation
  • Nickel / chemistry*
  • Organometallic Compounds / chemistry*
  • Piperazine
  • Piperazines / chemistry*

Substances

  • Bridged-Ring Compounds
  • Organometallic Compounds
  • Piperazines
  • Piperazine
  • Nickel
  • tetramethylenedisulfotetramine