Bis(n-pentanethiolato)mercury(II), Hg(SC₅H₁₁)₂ - Preparation, Characterization, Crystal and Molecular Structure; Reactivity towards Organic Thiols

Abstract

Crystal structure, IR Data, Raman Data, Mass Spectrum, Bis(/2-pentanethiolato)mercury(II)The preparation of bis(/?-pentanethiolato)mercury(II), Hg(SC5Hn)2, and n-pentanethiolatomercury(II) iodide, IH gSC sH n, starting from H gl2 and rc-pentanethiol, is presented; the X-ray crystal structure determination of Hg(SC5H n)2 reveals a layered structure of the bis(thiolate) molecule. With 178.69(1.02)° the S-H g-S moiety is nearly linear. The Hg-S bond length is shorter then the sum of the covalent radii of sulphur and mercury atoms indicating a primary co-ordination number of two, which is supported by the IR and Raman spectra. Assignments of i/Sym(Hg-S) and i'asym(Hg-S) are given. The mass spectrum reveals the title compound to be monomeric in the gas phase. Melting and thermal decomposition have been investigated by DTA methods. The behaviour towards organic thiols is discussed. In addition, IR and Raman spectroscopic data of IH gSCsHn are presented and discussed.

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

“…The following compounds could be detected using GC/MS: (1) C3H7SSC3H7 (M + ) 150), (2) C3H7SSC7H15 (M + ) 206), (3) 3 (M + ) 350; Hg isotope pattern), (4) C7H15SSC7H15 (M + ) 262), (5) C3H7SHgSC7H15 (12) (M + ) 406; Hg isotope pattern), and (6) 7 (M + ) 462; Hg isotope pattern). Additionally, the following compounds were formed in very low concentrations as decomposition products, mainly caused by the high temperatures applied during the GC/MS investigations: 18 (7) C3H7SC3H7 (M + ) 118), (8) C3H7SSSC3H7 (M + ) 182), (9) C7H15SC7H15 (M + ) 230), and (10) C7H15SSSC7H15 (M + ) 294). After 384 h, excess C7H15SSC7H15 was added to the reaction mixture.…”

“…Because of scarce and even poor structural data (further refinements of the structural data of some compounds seem to be necessary) available for these compounds, [13][14][15][16][17][18][19] the solidstate vibrational spectra are of special interest, too, 20 so much the more as some controversial discussions with respect to the assignments of fundamental vibrations still exist. 21,22a In addition, 1 H NMR spectroscopic data of these homoleptic compounds do not contribute spectacular knowledge.…”

Structural characterization of 1,3-propanedithiols that feature carboxylic acids: Homologues of mercury chelating agents

“…In view of the well-known affinity of mercury for sulfur, as illustrated by the fact that mercury forms compounds with a diverse array of sulfur donor ligands (including thiolate [10-12], thioether [13] and thione [14,15] derivatives), much attention has been directed towards the use of sulfur-containing ligands in chelation therapy [1-3]. For example, a common feature of the chelating agents illustrated in Fig.…”

9 Zinc, cadmium and mercury

“…63 The molecular structure has been determined for [Hg(SC 5 H 11 ) 2 ] formed by reaction of HgI 2 with n-pentanethiol. 64 Crystal structures have been reported for [Hg(S 2 CNRR H ) 2 ] (R R H Bu i ; R Pr i , R H Cy; R Et, R H Cy; R R H Bu n ), with a discussion of the importance of considering crystal structures when rationalising molecular structures. 65 67 The crystal structure for [Hg(Ph)(pytd)]Ádmso shows the mercury atom to be co-ordinated to a phenyl carbon, the thiohydantoin nitrogen and the pyridine nitrogen in an overall T-shaped arrangement, but there are also weak Hg Á Á Á S interactions, one intra-and one inter-molecular.…”