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Journal ArticleDOI

Synthesis, properties and crystal structure of bis(thiobenzoato-s) selenium(II)

01 Jan 1983-Polyhedron (Pergamon)-Vol. 2, Iss: 10, pp 1025-1029
TL;DR: The synthesis, properties and crystal structure of bis(thiobenzoato)selenium(II) are described in this article, which is formed on interaction of selenium(IV) in acid medium with thiobenzzoic acid.
About: This article is published in Polyhedron.The article was published on 1983-01-01. It has received 5 citations till now. The article focuses on the topics: Selenium & Crystal structure.
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Journal ArticleDOI
TL;DR: MP2/LANL2DZ(d) geometry optimizations, single point energy and frequency calculations performed for Se(SMe)(2) show, that syn- and anti-conformers (C(2) represent minima on the potential energy surface, the latter being by 8 kJ mol(-1) lower in energy than the former.
Abstract: Selenium(II) dimethanethiolate, Se(SMe)2, was synthesized by reaction of SeO2 with HSMe. Basic spectroscopic data for Se(SMe)2 and selenium(II) bis(2-methyl-2-propanethiolate), Se(StBu)2, were recorded and interpreted with the support of ab initio calculations. Both compounds are thermodynamically unstable relatively to selenium and the corresponding disulfide. The UV/vis spectra of both compounds are qualitatively similar, the two bands being attributed to n(Se)–σ*(Se–S) transitions. The bands at 369 and 397 cm−1 in the IR spectra of Se(SMe)2 and Se(StBu)2, respectively, are assigned to νas(SeS2). The 77Se NMR shifts of Se(SMe)2 (784 ppm) and Se(StBu)2 (556 ppm) differ substantially from each other and show positive temperature gradients. Calculations at the GIAO-HF/962+(d) level reproduced the difference of the 77Se NMR chemical shifts between Se(SMe)2 and Se(StBu)2. At the same level, the effect of conformational changes on 77Se shifts were studied for Se(SMe)2. In the solid state Se(SMe)2 forms long intermolecular Se⋯S contacts while Se(StBu)2 does not. Both compounds exhibit anti-conformations of the methyl and tert-butyl groups with respect to the SeS2 plane. MP2/LANL2DZ(d) geometry optimizations, single point energy and frequency calculations performed for Se(SMe)2 show, that syn- (Cs) and anti-conformers (C2) represent minima on the potential energy surface, the latter being by 8 kJ mol−1 lower in energy than the former. Both conformers are stabilized by intramolecular π-type n(S1)–σ*(Se–S2) orbital interactions. The energy of the transition state for the mutual conversion of the two conformers was calculated to be 31 kJ mol−1 above that of the syn conformer, allowing a rapid interconversion of the two conformers at room temperature. Intermolecular interactions between Se(SMe)2 molecules were also studied by means of calculations at the MP2/LANL2DZ(d) level. For Se(StBu)2 MP2/LANL2DZ(d) geometry optimizations and single point energy calculations revealed a C2-symmetric anti- and a C1 symmetric syn-conformer, the latter being 21 kJ mol−1 higher in energy than the former. Se(SMe)2 and Se(StBu)2 exchange thiolate groups with other selenium(II) dithiolates, tellurium(II) dithiolates and with thiols, if catalytic amounts of p-CH3C6H4SO3H are added.

11 citations

Journal ArticleDOI
TL;DR: In this article, a single-source reagent Me3Si−SeS−SiMe3 is used to distribute Se2− and S2− to the metal core as a redox reaction occurs.
Abstract: Mercury-selenosulfide (HgSexS1-x) nanoparticles have been synthesized using the single-source reagent Me3Si–SeS–SiMe3. The reagent distributes Se2− and S2− to the metal core as the reaction between Me3Si–SeS–SiMe3 and mercury acetate occurs via a redox pathway, ultimately giving rise to Se–S bond cleavage. Particles are characterized by EDX, TEM and powder X-ray diffraction analysis in conjunction with UV–Visible absorption spectroscopy.

8 citations

Journal ArticleDOI
TL;DR: In this article, the X-ray crystal structure determination of ditritylseleno trisulfide was obtained by reacting trityl thiol 6 with the first selenium transfer reagent bis-benzotriazol-1-yl selenide 7.
Abstract: The X-ray crystal structure determination of ditritylseleno trisulfide 5 was obtained. C 38 H 30 S 2 Se, Mr=629.74, monoclinic, p 2 1 / n , a =14.078(4), b =12.852(4), c =17.171(6) A, β=98.08(2)°. V =3070.7 A 3 , Z =4, Do=1.37 g/cm 3 , MoK α , λ=0.71069 A, μ=14.66 cm −1 , F (000)=370, T =293(2) K, R ( R w )=0.0355(0.0342) for 2895 observed independent reflections [ F >2.5σ( F )], goodness of fit=1.104. The material was obtained by reacting trityl thiol 6 with the first selenium transfer reagent bis- N -benzotriazol-1-yl selenide 7 .

3 citations

Journal ArticleDOI
TL;DR: Natural bond orbital analyses of dithio-compounds revealed that two types of orbital interactions play a role in the bonding of E[S(2)S(1)CC(6)H(4)OMe-2](2) (E = Se, Te) and the former play a particularly predominant role.
Abstract: A series of selenium and tellurium bis(carbodithioates and carbothioates) were synthesized. X-Ray structure analysis revealed that Se(SSCC6H4OMe-2)2, Te(SSCC6H4OMe-2)2 and Te(SSCC6H4Me-4)2 have trapezoidal-planar configuration of ES4 (E = Se, Te) and despite the larger atomic radii, the CS⋯Te distances in Te(SSCC6H4OMe-2)2 are comparable to those in the corresponding selenium derivatives Se(SSCC6H4OMe-2)2. Molecular-orbital calculations performed on compounds E(E′SCR)2 (E = S, Se, Te; E′ = O, S; R = Me, Ph, C6H4OMe-2) showed that the syn-conformers of Se(SSCR)2 and Te(SSCR)2 are more stable than the corresponding anti-ones, while, in the case of carbothioic acid derivatives, E(SOCR)2 showed that their anti-conformers are all more stable than the corresponding syn-ones. Natural bond orbital (NBO) analyses of these dithio-compounds revealed that two types of orbital interactions, nS(1)→σ*E–S(2) and nO→σ*E–S(2), play a role in the bonding of E[S(2)S(1)CC6H4OMe-2]2 (E = Se, Te) and the former play a particularly predominant role.

2 citations

Journal ArticleDOI
TL;DR: The synthesis and crystal structure of bis(o-phenylenethiourea)selenium(II)-chloride dihydrate, Se(C7H6N2S)2Cl2·2H2O are reported in this article.
Abstract: The synthesis and crystal structure ofbis(o-phenylenethiourea)selenium(II)-chloride dihydrate, Se(C7H6N2S)2Cl2·2H2O are reported. The compound crystallizes in the monoclinic space group, P21/n, with four molecules per unit cell, the dimensions of which area=10.243(3),b=13.341(4),c=14.273(4) A,β=93.00(3)°,U=1947.76 A3. The structure was solved by direct methods and refined by full-matrix least-squares toR=0.039 andR w =0.040 for 3314 unique reflections. Selenium displays two strong coordinations arising from the two sulfurs, Se-S(1)=2.191(1), Se-S(2)=2.206(1) A, and S(1)-Se-S(2)=101.0(1)°, and four secondary interactions involving three chlorines and one sulfur. The complex occurs as a dimer with two sets of very weakly interacting bridging pairs S(2), S(2)a; and Cl(2), Cl(2)a, where “a” denotes the inversion related atom. Lattice stabilization is ensured by the extensive network of hydrogen bonds involving chlorines, water oxygens, and nitrogens of phenylenethiourea ligands.
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