Ligand-exchange processes on solvated zinc cations: water exchange on [Zn(H2O)4(L)]2+.2H2O (L=heterocyclic ligand)

Chemistry. 2010 Jun 25;16(24):7300-8. doi: 10.1002/chem.200902264.

Abstract

The water-exchange mechanisms of [Zn(H(2)O)(4)(L)](2+).2H(2)O (L=imidazole, pyrazole, 1,2,4-triazole, pyridine, 4-cyanopyridine, 4-aminopyridine, 2-azaphosphole, 2-azafuran, 2-azathiophene, and 2-azaselenophene) have been investigated by DFT calculations (RB3LYP/6-311+G**). The results support limiting associative reaction pathways that involve the formation of six-coordinate intermediates [Zn(H(2)O)(5)(L)](2+).H(2)O. The basicity of the coordinated heterocyclic ligands shows a good correlation with the activation barriers, structural parameters, and stability of the transition and intermediate states.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cations / chemistry*
  • Crystallography, X-Ray
  • Heterocyclic Compounds / chemistry*
  • Hydrogen-Ion Concentration
  • Ligands
  • Molecular Structure
  • Organometallic Compounds / chemistry*
  • Solvents / chemistry*
  • Water / chemistry*
  • Zinc / chemistry*

Substances

  • Cations
  • Heterocyclic Compounds
  • Ligands
  • Organometallic Compounds
  • Solvents
  • Water
  • Zinc