Solid-state structure and solution behaviour of organomercury(II) compounds containing 2-(Me2NCH2)C6H4- moieties. Supramolecular aspects

摘要

The reaction of [2-(Me2NCH2)C6H4] HgCl (1) with NH4Br and KI gave the analogous bromide (2) and iodide (3), respectively. To investigate the competitive coordination to the mercury centre of the nitrogen atom of the pendant arm and the donor atoms of a potentially chelating anionic ligand the dithiocarbamates [2-(Me2NCH2) C6H4] HgS(S) CNR2 [R = Me (4), Et (5)] were prepared by reacting 1 with Na[S2CNR2]center dot nH(2)O (R = Me, n = 2; R = Et, n = 3). The reaction between PhHgCl and the same sodium dithiocarbamates afforded PhHgS(S) CNR2 [R = Me (6), Et (7)]. The compounds were investigated by multinuclear NMR spectroscopy (H-1, C-13, Hg-199 and 2D experiments) and mass spectrometry. The solid- state molecular structures of compounds 2- 6 were established by single- crystal X- ray diffraction. In the compounds 2-5 the nitrogen atom of the pendant CH2NMe2 arm is strongly coordinated to the mercury atom. The (C,N)HgX core is non-planar in the dithiocarbamates 4 and 5 and thus the mercury atom becomes a stereocentre. Supramolecular associations based on Hg center dot center dot center dot X, Hg center dot center dot center dot S, C-H center dot center dot center dot X (X = Br, I), S center dot center dot center dot S and C-H center dot center dot center dot pi interactions are discussed. (C) 2017 Elsevier B.V. All rights reserved.