Bis(trimethylsilyl)sulfide

{{Chembox

| Watchedfields = changed

| verifiedrevid = 401708703

| ImageFile = S(tms)2.svg

| ImageSize = 240px

| ImageName = Stereo structural formula of bis(trimethylsilyl)sulfide

| ImageFileL1 = Bis(trimethylsilyl)sulfide-3D-balls.png

| ImageFileR1 = Bis(trimethylsilyl)sulfide-3D-spacefill.png

| PIN = Hexamethyldisilathiane

| OtherNames = Trimethyl[(trimethylsilyl)sulfanyl]silane

|Section1={{Chembox Identifiers

| CASNo = 3385-94-2

| CASNo_Ref = {{cascite|correct|??}}

| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = AZ6L5QJY5H

| PubChem = 76920

| ChemSpiderID = 69371

| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

| EINECS = 222-201-4

| UNNumber = 1993

| SMILES = C[Si](C)(C)S[Si](C)(C)C

| SMILES1 = S([Si](C)(C)C)[Si](C)(C)C

| StdInChI_Ref = {{stdinchicite|correct|chemspider}}

| StdInChI = 1S/C6H18SSi2/c1-8(2,3)7-9(4,5)6/h1-6H3

| InChI = 1/C6H18SSi2/c1-8(2,3)7-9(4,5)6/h1-6H3

| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

| StdInChIKey = RLECCBFNWDXKPK-UHFFFAOYSA-N

| InChIKey = RLECCBFNWDXKPK-UHFFFAOYAN

| Beilstein = 1698358}}

|Section2={{Chembox Properties

| C=6 | H=18 | Si=2 | S=1

| Appearance = colourless liquid with foul odor

| Density = 0.846 g cm−3

| Solubility = hydrolyzes

| Solvent = other solvents

| SolubleOther = ethers such as THF
and arenes such as toluene
mastersearch.chemexper.com/cheminfo/servlet/org.dbcreator.MainServlet

| BoilingPtC = 163

| RefractIndex = 1.4586}}

|Section3={{Chembox Structure

| Dipole = 1.85 D

}}

|Section7={{Chembox Hazards

| ExternalSDS = [http://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=US&language=en&productNumber=283134&brand=ALDRICH&PageToGoToURL=http%3A%2F%2Fwww.sigmaaldrich.com%2Fcatalog%2Fproduct%2Faldrich%2F283134%3Flang%3Den "External MSDS"]

| MainHazards = Toxic

| GHSPictograms = {{GHS skull and crossbones}} {{GHS flame}}

| GHSSignalWord = Danger

| HPhrases = {{H-phrases|226|331|311|301||}}[http://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=US&language=en&productNumber=283134&brand=ALDRICH&PageToGoToURL=http%3A%2F%2Fwww.sigmaaldrich.com%2Fcatalog%2Fproduct%2Faldrich%2F283134%3Flang%3Den Product catalog] sigmaaldrich.com {{dead link|date=March 2024}}

| PPhrases = {{P-phrases|261|280|301+310|311}}

| NFPA-H=2|NFPA-F=3|NFPA-R=0|NFPA-S=

}}

|Section8={{Chembox Related

| OtherCompounds = B2S3, SiS2

}}

}}

Bis(trimethylsilyl) sulfide is the chemical compound with the formula ((CH3)3Si)2S. Often abbreviated (tms)2S, this colourless, vile-smelling liquid is a useful aprotic source of "S2−" in chemical synthesis.{{cite journal|author=Matulenko, M. A. |title=Bis(trimethylsilyl) Sulfide|journal= Encyclopedia of Reagents for Organic Synthesis |year =2004 |doi = 10.1002/047084289X |volume=1 |pages=5|hdl=10261/236866 |isbn=9780471936237|url=https://hal.archives-ouvertes.fr/hal-02922790|hdl-access=free }}

Synthesis

The reagent is prepared by treating trimethylsilyl chloride with anhydrous sodium sulfide:{{cite book |author1=So, J.-H. |author2=Boudjouk, P. | chapter = Hexamethyldisilathiane | title = Inorganic Syntheses | editor = Russell, N. G. | year = 1992 | volume = 29 | isbn = 0-471-54470-1 | doi = 10.1002/9780470132609.ch11 | page = 30 | publisher = Wiley | location = New York}}

:2 (CH3)3SiCl + Na2S → ((CH3)3Si)2S + 2 NaCl

((CH3)3Si)2S must be protected from air because it hydrolyzes readily:

:((CH3)3Si)2S + H2O → ((CH3)3Si)2O + H2S

Use in synthesis

Bis(trimethylsilyl)sulfide is a reagent for the conversion of metal oxides and chlorides into the corresponding sulfides.Lee, S. C.; Holm, R. H., "Nonmolecular Metal Chalcogenide/Halide Solids and Their Molecular Cluster Analogues", Angewandte Chemie International Edition in English, 1990, volume 29, pages 840-856. This transformation exploits the affinity of silicon(IV) for oxygen and halides. An idealized reaction is:

:((CH3)3Si)2S + MO → ((CH3)3Si)2O + MS

In a similar way, it has been used in the conversion of aldehydes and ketones to the corresponding thiones.{{cite journal| title = Synthetic Applications of Bis(trimethylsilyl)sulfide: Part II. Synthesis of Aromatic and Heteroaromatic o-Azido-Thioaldehydes|author1=A. Capperucci |author2=A. Degl'Innocenti |author3=P. Scafato |author4=P. Spagnolo | journal = Chemistry Letters| volume = 24| pages = 147| year = 1995| doi = 10.1246/cl.1995.147| issue = 2}}{{cite journal| title = Some Recent Synthetic Routes to Thioketones and Thioaldehydes|author1=W. M. McGregor |author2=D. C. Sherrington | journal = Chemical Society Reviews| volume = 22| pages = 199–204| year = 1993| doi = 10.1039/CS9932200199| issue = 3}}

Image:ASUTAJ = CCDB code. Ag-S nanocrystal as described in doi 10.1002SLASHanie.200352351.png

Safety

((CH3)3Si)2S reacts exothermically with water, releasing toxic H2S.

References