Complexation of 7-azaindole by the methylmercury(II) cation

Abstract

Complexes of the types [CH3Hg(aza)], [CH3Hg(Haza)]X, and [(CH3Hg)2(aza)]X are obtained by reacting CH3HgOH and/or CH3HgX (X = NO3, ClO4) with 7-azaindole (Haza). The weakly acidic N1-H proton on the pyrrole ring is displaced by the hydroxide, whereas the perchlorate and nitrate salts lead to CH3Hg+ coordination to the N7 lone pair on the pyridine ring. Detailed analysis of the infrared spectra of the complexes and their N-deuterated derivatives provides diagnostic regions for eventual prediction of the coordination mode in other systems. All compounds are characterized by means of 1H, 13C, and 199Hg NMR spectra in DMSO solution and solid-state CP-MAS 13C spectra. Comparison of the solution and solid-state 13C spectra show that the species present in the solids remain undissociated in DMSO. Each type of complex can be identified from a characteristic pattern of large displacements of the ligand 13C signals. The 1H spectra are less informative because substitution of the N1-H proton by CH3Hg+ induces only minor shifts. Metal solvation appears to have a major influence on the 13C and 199Hg chemical shifts of the CH3Hg+ groups.