| Revision as of 14:20, 6 December 2011 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 450710655 of page Silylene for the Chem/Drugbox validation project (updated: ''). |
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{Chembox |
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{{Chembox |
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|Name = generic silylene |
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|Watchedfields = changed |
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| verifiedrevid = 404979853 |
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| IUPACName = Silylene |
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|ImageFile = Silylene.svg |
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|ImageFile1 = Silylene-3D-vdW.png |
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| SystematicName = Silylidene{{Reference necessary|date = March 2011}} |
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|ImageCaption = Simplest silylene has R=Hydrogen |
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| OtherNames = Hydrogen silicide(-II)<br /> |
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|verifiedrevid = 464391717 |
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Silicene<br /> |
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|IUPACName = Silylene |
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| Section1 = {{Chembox Identifiers |
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|SystematicName = Silylidene<ref>{{BlueBook2013|rec=71.2.2.1}}</ref> |
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| PubChem = 6327230 |
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|OtherNames = Hydrogen silicide(−II)<br />Silicene |
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| PubChem_Ref = {{Pubchemcite|correct|PubChem}} |
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|Section1 = {{Chembox Identifiers |
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| ChemSpiderID = 4885758 |
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|CASNo = 13825-90-6 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|PubChem = 6327230 |
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| SMILES = |
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|ChemSpiderID = 4885758 |
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| StdInChI = 1S/H2Si/h1H2 |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|SMILES = |
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| StdInChIKey = XMIJDTGORVPYLW-UHFFFAOYSA-N |
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|StdInChI = 1S/H2Si/h1H2 |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChIKey = XMIJDTGORVPYLW-UHFFFAOYSA-N |
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|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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}} |
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| Section2 = {{Chembox Properties |
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|Section2 = {{Chembox Properties |
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| H = 2 |
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| H = 2 | Si = 1 |
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| Si = 1 |
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| ExactMass = 29.992576597 g mol<sup>-1</sup> |
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'''Silylene''' is a ] with the formula SiR<sub>2</sub>. It is the ] analog of ]. Due to presence of a vacant p orbital, silylene rapidly reacts in a bimolecular manner{{clarify|date=October 2020|reason=Does it dimerise? (to a silene?) polymerise?}} when condensed. Unlike carbenes, which can exist in the ] or ] state, silylene (and all of its derivatives) are singlets. |
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'''Silylenes''' are formal derivatives of silylene with its hydrogens replaced by other substituents.<ref>{{cite journal |doi=10.1021/cr900093s |title=Stable Heavier Carbene Analogues |year=2009 |last1=Mizuhata |first1=Yoshiyuki |last2=Sasamori |first2=Takahiro |last3=Tokitoh |first3=Norihiro |journal=Chemical Reviews |volume=109 |issue=8 |pages=3479–3511 |pmid=19630390 }}</ref> Most examples feature amido (NR<sub>2</sub>) or alkyl/aryl groups.<ref name=HR>{{cite journal |doi=10.1021/om7007869|title=The Chemistry of Aluminum(I), Silicon(II), and Germanium(II) |year=2008 |last1=Nagendran |first1=Selvarajan|last2=Roesky|first2=Herbert W.|journal=Organometallics|volume=27|issue=4|pages=457–492}}</ref><ref name=denk1>{{cite journal |doi=10.1021/ar950192g|title=Stable Silylenes|year=2000|last1=Haaf|first1=Michael|last2=Schmedake|first2=Thomas A.|last3=West|first3=Robert|journal=Accounts of Chemical Research|volume=33|issue=10|pages=704–714|pmid=11041835}}</ref> |
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Silylenes have been proposed as ]s. They are ]s.<ref>{{cite book |doi=10.1002/0470857250.ch43 |chapter=Silylenes |year=1998 |last1=Gaspar |first1=Peter |last2=West |first2=R. |title=The Chemistry of Organic Silicon Compounds |series=The Chemistry of Functional Groups |volume=2 |issue=1 |pages=2463–2568 |isbn=0471967572 }}</ref> |
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==Synthesis and properties== |
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Silylenes are generally synthesized by ] or ] of ]s, by ] atom reactions (], ] or abstraction), by ] of ]s, or by ] of 1,1-dihalosilane. It has long been assumed that the conversion of metallic Si to tetravalent silicon compounds proceeds via silylene intermediates: |
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:Si + Cl<sub>2</sub> → SiCl<sub>2</sub> |
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:SiCl<sub>2</sub> + Cl<sub>2</sub> → SiCl<sub>4</sub> |
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Similar considerations apply to the ], the reaction of ] and bulk silicon. |
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Early observations of silylenes involved generation of dimethylsilylene by dechlorination of ]:<ref>{{cite journal |doi=10.1021/ja01061a040|title=Dimethylsilene: CH<sub>3</sub>SiCH<sub>3</sub>|year=1964|last1=Skell|first1=P. S.|last2=Goldstein|first2=E. J.|journal=Journal of the American Chemical Society|volume=86|issue=7|pages=1442–1443}}</ref> |
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:SiCl<sub>2</sub>(CH<sub>3</sub>)<sub>2</sub> + 2 K → Si(CH<sub>3</sub>)<sub>2</sub> + 2 KCl |
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The formation of dimethylsilylene was demonstrated by conducting the dechlorination in the presence of ], the ] product being pentamethyldisilane: |
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:Si(CH<sub>3</sub>)<sub>2</sub> + HSi(CH<sub>3</sub>)<sub>3</sub> → (CH<sub>3</sub>)<sub>2</sub>Si(H)−Si(CH<sub>3</sub>)<sub>3</sub> |
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A room-temperature isolable ] is {{chem name|''N'',''N''′-di-''tert''-butyl-1,3-diaza-2-silacyclopent-4-en-2-ylidene}}, first described in 1994 by ] et al.<ref>{{cite journal |doi=10.1021/ja00085a088|title=Synthesis and Structure of a Stable Silylene|year=1994|last1=Denk|first1=Michael|last2=Lennon|first2=Robert|last3=Hayashi|first3=Randy|last4=West|first4=Robert|last5=Belyakov|first5=Alexander V.|last6=Verne|first6=Hans P.|last7=Haaland|first7=Arne|last8=Wagner|first8=Matthias|last9=Metzler|first9=Nils|journal=Journal of the American Chemical Society|volume=116|issue=6|pages=2691–2692}}</ref> |
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] |
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The α-amido centers stabilize silylenes by π-donation. The dehalogenation of diorganosilicon dihalides is a widely exploited.<ref>{{cite journal |doi=10.1021/ja062928i|title=A New Type of ''N''-Heterocyclic Silylene with Ambivalent Reactivity|year=2006|last1=Driess|first1=Matthias|last2=Yao|first2=Shenglai|last3=Brym|first3=Markus|last4=Van Wüllen|first4=Christoph|last5=Lentz|first5=Dieter|journal=Journal of the American Chemical Society|volume=128|issue=30|pages=9628–9629|pmid=16866506}}</ref> |
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==Related reactions== |
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] is an example of a silylene.<ref name=HR/>]]In one study diphenylsilylene is generated by ] of a trisilane:<ref>{{cite journal |doi=10.1021/ja0653223|title=Diphenylsilylene|year=2006|last1=Moiseev|first1=Andrey G.|last2=Leigh|first2=William J.|journal=Journal of the American Chemical Society|volume=128|issue=45|pages=14442–14443|pmid=17090011}}</ref> |
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:] |
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In this reaction diphenylsilylene is extruded from the trisila ring. The silylene can be observed with ] at 520 nm and is short-lived with a ] of two ]s. Added ] acts as a ] with a ] of {{val|1.3e10|u=mol<sup>−1</sup> s<sup>−1</sup>}} which is close to diffusion control. |
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==See also== |
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*] |
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*] |
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*], R<sub>2</sub>Si=SiR<sub>2</sub> |
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*]s, protonated silylenes |
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==References== |
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{{Reflist}} |
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] |
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] |