Cysteamine and its homoleptic complexes with group 12 metal ions. Differences in the coordination chemistry of ZnII, CdII, and HgII with a small N,S-donor ligand.
2-Ammoniumethanethiolate, (-)SCH(2)CH(2)NH(3)(+), the first structurally characterized zwitterionic ammoniumthiolate, is the stable form of cysteamine (HL) in the solid state and in aqueous solution. Reactions of ZnCl(2), Cd(Oac)(2), and HgCl(2) with cysteamine and NaOH in a 1:2:2 ratio, respectively, lead to the homoleptic complexes ML(2). Their single-crystal X-ray structures demonstrate basic differences in the coordination chemistry of Zn(II), Cd(II), and Hg(II). While chelating N,S-coordination modes are found for all metal ions, Zn(II) forms a mononuclear complex with a distorted tetrahedral Zn(N(2)S(2)) coordination mode, whereas Hg(II) displays a dimer with Hg(N(2)S(2)) coordinated monomers being connected by two long Hg...S contacts. Solid-state (199)Hg NMR spectra of HgL(2) and [Hg(HL)(2)]Cl(2) reveal a low-field shift of the signals with increasing coordination number. Strong and nearly symmetric Cd-S-Cd bridges in solid CdL(2) lead to a chain structure, Cd(II) displaying a distorted square pyramidal Cd(N(2)S(3)) coordination mode. The ab initio [MP2/LANL2DZ(d,f)] structures of isolated ML(2) show a change from a distorted tetrahedral to bisphenoidal coordination mode in the sequence Zn(II)-Cd(II)-Hg(II). A natural bond orbital analysis showed a high ionic character for the M-S bonds and suggests that the S-M-S fragment is best described by a 3c4e bond. The strength of the M...N interactions and the stability of ML(2) toward decomposition to M and L-L decreases in the sequence Zn > Cd > Hg. Ab initio calculations further suggest that a tetrahedral S-M-S angle stabilizes Zn(II) against substitution by Cd(II) and Hg(II) in a M(N(2)S(2)) environment. Such geometry is provided in zinc-finger proteins, as was found by a database survey.
Fleischer
Holger
H
Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg Universität Mainz, Germany. fleische@uni-mainz.de
Dienes
Yvonne
Y
Mathiasch
Bernd
B
Schmitt
Volker
V
Schollmeyer
Dieter
D