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.
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