Bis(n-alkanethiolato)mercury(II) Compounds, Hg(SC_nH_2n+1)₂ (n = 1 to 10, 12):  Preparation Methods, Vibrational Spectra, GC/MS Investigations, and Exchange Reactions with Diorganyl Disulfides

Abstract

Several preparative routes to bis(n-alkanethiolato)mercury(II) compounds of the general composition Hg(SC n H2 n +1)2 for n = 1−10, 12 (compounds 1 − 11, respectively) are presented, including the reaction of mercury(II) iodide with n-alkanethiols and triethylamine as an auxiliary base, as well as the reaction of mercury(II) chloride with trimethylsilyl methyl sulfide as an example for this particular type of exchange reaction using trimethylsilyl sulfides as thiolate transferring reagents. With respect to the possibility of mobilizing these compounds into the environment under special natural surroundings, as for example found in some natural gas reservoirs, the reactivity of the title compounds toward excess di-n-alkyl disulfides leading to the exchange of the thiolate functional groups of both the mercury compounds and the disulfides is investigated. Equilibration reactions of specifically stoichiometric amounts of Hg(SC3H7)2 (3) and C7H15SSC7H15, as well as Hg(SC7H15)2 (7) and C3H7SSC3H7 are investigated in more detail using the coupling of gas chromatography and mass spectrometry (GC/MS). The FT-IR and FT-Raman spectroscopic data of the solid title compounds are given and discussed. Assignments of νs(Hg−S) and νas(Hg−S) stretchings, as well as δ(C−S−Hg) and δ(S−Hg−S) bendings are reported and discussed in comparison to literature data. The spectroscopic data suggest mercury to be two-coordinated in all studied compounds with the exception of Hg(SC4H9)2 (4). This particular compound obviously contains a four-coordinated central mercury atom. The title compounds were analyzed by means of GC/MS, which indicated that the compounds (i) decompose at elevated temperatures, mainly to form mercury and the corresponding disulfide, and (ii) are monomer in the gas phase.

Ion-imprinted beads for molecular recognition based mercury removal from human serum

“…Hoffmann et al investigated FTIR and FT-Raman spectroscopy for Hg(SR) 2 compounds in the solid state [30]. Their results show that the frequency window of the Hg-S-stretching vibrations is approximately 400-180 cm −1 .…”

Conducting Polymer Matrix Poly(2,2′-bithiophene) Mercury Metal Incorporation

“…Moreover, a new weak peak emerges at 189 cm À1 upon Hg uptake into the polymer matrix and does not overlap with any of the TBATFB contributions. It was attributed to a C-S-Hg bending mode (Hoffmann, Brockner, and Steinfatt 2001).…”

Synthesis, Spectral and Thermal Characterization of Bis(pyridine-3- carboxy-2-thiolato-S)mercury(II). Crystal Structure of Dibromobis(3- metoxycarbonylpyridine-2-thiolato-S)mercury(II)

“…42 Position of the Hg−S stretching mode depends on the coordination number of mercury. In the Raman spectrum of Hg(Hmna) 2 the medium band at 378 cm 1 is observed.…”