Carbon sulfide selenide
| Names | |
|---|---|
| IUPAC name
selanylidenemethanethione | |
| Identifiers | |
3D model (JSmol) |
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| ChemSpider | |
PubChem CID |
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| Properties | |
| CSSe | |
| Molar mass | 123.04 g·mol−1 |
| Related compounds | |
Related compounds |
carbon diselenide |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Carbon sulfide selenide or thiocarbonyl selenide is a triatomic molecular compound with formula S=C=Se.
Production
[edit]Carbon sulfide selenide was made by Henry Vincent Aird Briscoe by passing carbon disulfide vapour over ferrous selenide.[1]
- CS2 + FeSe → CSSe + FeS
Earlier it was made by passing an electric arc through liquid carbon disulfide in the presence of selenium.[1]
Properties
[edit]carbon sulfide selenide appears as a dark yellow oily liquid.[1] Its boiling point is about 83.92°C at 749.2 mmHg pressure.[1] The density of the liquid at 25° is 1.9777 Mg/m3.[1] Coefficient if cubic expansion is 0.000996.[1]
The liquid does not wet glass.[1] It is immiscible in water, but dissolves in acetone, benzene, bromoform or ethyl alcohol.[1]
The C-S bond length is 1.553 Å and the C-Se bond length is 1.695 Å[2]
The effect on humans is lachrymatory, the vapour is extremely irritating to mucous membranes, and it smells disgusting.[1]
Microwave spectrum
[edit]| isotopolog | ground state rotational constant
MHz |
vibration‐rotation constant α2
MHz |
l‐type doubling constant
ql |
centrifugal distortion constant
Dj kHz |
|---|---|---|---|---|
| 32S12C76Se | 2078.190 | −4.215 | 1.041 | |
| 32S12C78Se | 2060.321 | −4.169 | 1.021 | 0.22 |
| 32S12C80Se | 2043.310 | −4.133 | 1.005 | 0.163 |
| 32S12C82Se | 2027.113 | −4.116 | 0.996 |
Molecular force field for C-Se: 5.72 mdyn/Å and C-S: 7.97 mdyn/Å. Dipole moment is 0.031 D.[3]
Reactions
[edit]Carbon sulfide selenide reacts with zinc and hydrochloric acid yielding hydrogen sulfide and hydrogen selenide.[1]
Carbon sulfide selenide reacts with dimethyl acetylenedicarboxylate under high pressure to yield a dithiadiselenafulvalene derivative.[4]
Reduction of carbon sulfide selenide forms a 1,3-dichalcogenole-2-chalcogenone-4,5-dichalcogenolate, but is a mixture of S and Se substances.[5] Selenium is in the 4,5 charged positions.[6]
A reaction with iodine and azide with carbon sulfide selenide results in the formation of selenium.[7]
Carbon sulfide selenide reacts with chlorine gas to form thiocarbonyl tetrachloride and selenium tetrachloride.[8] It does not react with iodine by itself, but only dissolves it.[8]
- CSSe + 4 Cl2 → ClSCCl3 + SeCl4
Carbon sulfide selenide reacts with bromine liquid to form thiocarbonyl tetrabromide and selenium tetrabromide and also some C2S2SeBr6.[8]
- CSSe + 4 Br2 → BrSCBr3 + SeBr4
Carbon sulfide selenide can complex with palladium. It reacts with Pd[P(CH(CH3)2)3]2, Pd[P(CH(CH3)2)3]3 or Pd[P(C6H5)3]4] to displace all but two of the ligands to add CSSe as a bidentate ligand. P(CH(CH3)2)3 also reacts with CSSe to yield [P(CH(CH3)2)3]+[CSSe]−. For these reactions, methanol can be a solvent.[9] C and Se atoms are ligands to the metal. The bonds in C=S and C=Se are lengthened in the ligand. The bond opposite to the C atom is lengthened.[9]
Complexes
[edit]| formula | name | structure | comment | reference |
|---|---|---|---|---|
| C5H5Co(PMe3)(η2-CSSe) | [9] | |||
| Pd[P(CH(CH3)2)3]2(η2-CSSe) | [9] | |||
| Pd[P(C6H5)3]2(η2-CSSe) | [9] | |||
| (diphos)Pd(η2-CSSe) | [9] | |||
| (dpmb)Pd(η2-CSSe) | P21/c a=9.585 b=15.02 c=21.50 Å β=103.1° | planar | [9] | |
| Os(η2-CSSe)(CO)(CN-p-tol)(PPh3)2 | [10] | |||
| Os(η2-CSeS)(CO)(CN-p-tol)(PPh3)2 | [10] | |||
| Ru(η2-CSSe)(CO)(CN-p-tol)(PPh3)2 | [10] | |||
| Ru(η2-CSeS)(CO)(CN-p-tol)(PPh3)2 | [10] | |||
References
[edit]- 1 2 3 4 5 6 7 8 9 10 Briscoe, Henry Vincent Aird; Peel, John Buttery; Robinson, Percy Lucock (1929). "X.—Carbon sulphidoselenide". J. Chem. Soc. 0: 56–60. doi:10.1039/JR9290000056.
- ↑ Harmony, M. D. (1979). Molecular Structures of Gas Phase Polyatomic Molecules Determined by Spectorscopic Methods (PDF). NIST. p. 667.
- 1 2 Hirose, Chiaki; Curl, R. F. (15 November 1971). "Microwave Spectrum, Molecular Structure, Force Field, and Dipole Moment of Thiocarbonyl Selenide, SCSe". The Journal of Chemical Physics. 55 (10): 5120–5123. Bibcode:1971JChPh..55.5120H. doi:10.1063/1.1675630. ISSN 0021-9606.
- ↑ Neochoritis, Constantinos; Zarganes-Tzitzikas, Tryfon; Stephanidou-Stephanatou, Julia (7 February 2014). "Dimethyl Acetylenedicarboxylate: A Versatile Tool in Organic Synthesis". Synthesis. 46 (5): 537–585. doi:10.1055/s-0033-1340615.
- ↑ Svenstrup, Niels; Becher, Jan (March 1995). "The Organic Chemistry of 1,3-Dithiole-2-thione-4,5-dithiolate (DMIT)". Synthesis. 1995 (3): 215–235. doi:10.1055/s-1995-3910.
- ↑ Hoyer, Eberhard (August 1983). "Facts and Fantasy on Tetrathio Oxalate—Activation and Condensation of Carbon Disulfide". Comments on Inorganic Chemistry. 2 (6): 261–270. doi:10.1080/02603598308078123.
- ↑ Jensen, K.A.; Pedersen, C. (1964). "1,2,3,4-Thiatriazoles". Advances in Heterocyclic Chemistry Volume 3. Vol. 3. pp. 263–284. doi:10.1016/S0065-2725(08)60544-9.
- 1 2 3 Briscoe, Henry Vincent Aird; Peel, John Buttery; Robinson, Percy Lucock (1929). "CXXXVII.—The reactions of the halogens with carbon sulphidoselenide". J. Chem. Soc. 0: 1048–1050. doi:10.1039/JR9290001048.
- 1 2 3 4 5 6 7 Werner, H.; Ebner, M.; Bertleff, W.; Schubert, U. (July 1983). "Complexes with carbon sulfides and selenides as ligands. Part 11. Reactions of (phosphine)palladium(0) complexes with thiocarbonyl selenide and the x-ray crystal structure of [1,2-C6H4(CH2PPh2)2]Pd(.eta.2-CSSe)". Organometallics. 2 (7): 891–895. doi:10.1021/om50001a019.
- 1 2 3 4 Brothers, P.J.; Headford, C.E.L.; Roper, W.R. (August 1980). "Geometrical isomerism arising from C,S- or C,Se- coordination of carbon selenide sulphide and the conversion of a thiocarbonyl ligand to a selenocarbonyl ligand". Journal of Organometallic Chemistry. 195 (3): C29–C33. doi:10.1016/S0022-328X(00)93322-9.