Structural, Spectroscopic, and Reactivity Properties of N 2 S 2 (thioether)‐O(amide)‐Ligated Hg II Complexes: The First Examples of Hg II ‐Mediated Amide Cleavage

Two mercury( II ) complexes [(bmppa)Hg(ClO 4 )]ClO 4 { 1 , bmppa = N,N ‐bis(2‐methylthio)ethyl‐ N ‐[(6‐pivaloylamido‐2‐pyridyl)methyl]amine} and [(beppa)Hg(ClO 4 )]ClO 4 { 2 , beppa = N,N ‐bis(2‐ethylthio)ethyl‐ N ‐[(6‐pivaloylamido‐2‐pyridyl)‐methyl]amine} of N 2 S 2 (thioether)O(amide)‐donor chelate ligands have been prepared and characterized by X‐ray crystallography and/or spectroscopic methods. In the solid state, the Hg II ion of 2 exhibits an overall coordination number of six and strong amide oxygen coordination. Comprehensive multinuclear NMR studies of 1 and 2 have yielded the first J     199 Hg   1 Hand J     199 Hg   13 Ccoupling constants associated with a Hg–RSCH 3 methyl group. In the presence of one equivalent of Me 4 NOH · 5H 2 O in methanol/acetonitrile solution, theamide appendages of 1 and 2 undergo alcoholysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)