Reactions of [Hg(Tab) 2 ](PF 6 ) 2 [Tab = 4‐(trimethylammonio)benzenethiolate] with NaX (X = Cl, NO 2 , NO 3 ): Isolation and Structural Characterization of a Series of Mono‐ and Binuclear Hg/Tab/X Compounds

Abstract

The complex [Hg(Tab)2](PF6)2 [Tab = 4-(trimethylammonio)benzenethiolate] (1) reacts with one or two equivalents of NaCl to afford the mononuclear complex [Hg(Tab)2Cl](PF6) (2) and the dinuclear complex [{Hg(μ-Tab)(Tab)Cl}2]Cl2·H2O (3·H2O), respectively. Similar reactions of 1 with NaCl and NaX (molar ratio = 1:1) produce the dinuclear species [{Hg(μ-Tab)(Tab)Cl}2]X2 [X = NO2 (4), NO3 (5)], while those with NaNO2 or NaNO3 give rise to [{Hg(μ-Tab)(Tab)X}2]X2 [X = NO2 (6), NO3 (7)]. Complexes 2–7 have been characterised by elemental analysis, IR, UV/Vis, and 1H NMR spectroscopy, and X-ray crystallography. The Hg atom of the [Hg(Tab)2Cl]+ cation in 2 adopts a T-shaped coordination geometry. Two [Hg(Tab)2Cl]+ cations in 3·H2O, 4, and 5 are linked by a pair of weak Hg–S bonds to form a dimeric [Hg(μ-Tab)(Tab)Cl]22+ dication, and the centrosymmetric [Hg(μ-Tab)(Tab)X]22+ dication in 6 and 7 consists of two [Hg(Tab)2X]+ cations linked by a couple of weak Hg–S bonds. The hydrogen-bonding interactions in 2–7 lead to the formation of interesting 2D (5, 7) or 3D (2–4, 6) hydrogen-bonded networks.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)