title: Ligand-exchange processes on solvated zinc cations: water exchange on [Zn(H2O)4(L)]2+.2H2O (L=heterocyclic ligand).
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.
authors.affiliation: Inorganic Chemistry, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany.
authors.forename: Basam M
authors.initials: BM
authors.lastname: Alzoubi
authors.forename: Ralph
authors.initials: R
authors.lastname: Puchta
authors.forename: Rudi
authors.initials: R
authors.lastname: van Eldik
mesh_terms: D002412:Cations / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D008024:Ligands; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D014867:Water / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: D002412:Cations; D006571:Heterocyclic Compounds; D008024:Ligands; D009942:Organometallic Compounds; D012997:Solvents; D014867:Water; D015032:Zinc