21094-80-4Relevant articles and documents
Syntheses and Vibrational Spectra of Some Tris(alkanethiolato)mercurate(II) Complexes, and Crystal Structure of the Hexakis-(methanethiolato)dimercurate(II) Dianion
Bowmaker, Graham A.,Dance, Ian G.,Dobson, Brian C.,Rogers, David Alan
, p. 1607 - 1618 (1984)
The complexes (R = Me, cation = Et4N+; R = But, cation = Et4N+, Bu4N+, +) have been prepared.The crystal structure of the methanethiolate complex shows that it contains centrosymmetric dinuclear anions 2- with distorted tetrahedral geometry about the mercury atoms.Vibrational spectroscopic evidence suggests that this complex dissociates on dissolution in ethanol to give mononuclear - species.The ButS- complexes appear to exist as mononuclear t)3>- species both in the solid state and in solution.The metal-sulfur stretching frequencies are assigned for all of the complexes studied, and the vibrational spectra are discussed in terms of the structures of the complex anions involved.Crystal data for 2Hg2(SCH3)6: a 8.656(5), b 9.130(6), c 12.368(8) Angstroem; α 102.16(4), β 105.51(4), γ 105.29(4) deg; space group P, Z 1, R 0.034, Rw 0.042.
Bis(n-alkanethiolato)mercury(II) compounds, Hg(SCnH2n+1)2 (n = 1 to 10, 12): Preparation methods, vibrational spectra, GC/MS investigations, and exchange reactions with diorganyl disulfides
Hoffmann,Brockner,Steinfatt
, p. 977 - 985 (2008/10/08)
Several preparative routes to bis(n-alkanethiolato)mercury(II) compounds of the general composition Hg(SCnH2n+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 vs(Hg-S) and vas(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.
