Nucleophilicity of zinc-bound thiolates

Delphine Picot (1) , Gilles Ohanessian (1) , Gilles Frison (1)

1 DCMR - Laboratoire des mécanismes réactionnels

The nucleophilicity of biomimetic zinc-thiolate complexes against methyl iodide has been studied. The activation barrier has been computed with the B3LYP functional. The reactivity depends on the global charge, the nature of the ligand set and the presence of hydrogen bonds. This shows that the understanding of zinc site nucleophilicity cannot be achieved by the knowledge of the atom donor set for zinc only, as currently done in the literature. Moreover, we show that sulfur proton affinity and activation barrier are directly proportional, thus providing a good nucleophilicity index for zinc-bound thiolate.

Mots clés: Density functional calculations; Zinc; Nucleophilicity; Hydrogen bonds; S ligands; Tridentate ligands; Bioinorganic chemistry

Domaines: Chimie théorique et/ou physique; Chimie inorganique; Chimie de coordination

Delphine Picot, Gilles Ohanessian, Gilles Frison. Nucleophilicity of zinc-bound thiolates. Comptes Rendus. Chimie, 2009, 12, pp.546-553. ⟨10.1016/j.crci.2009.01.002⟩. ⟨hal-00462197⟩