查看“︁三(三甲基硅基)胺”︁的源代码

{{Chembox
<!-- Images -->| Name           = 
| ImageFile      = Tris(trimethylsilyl)amin Strukturformel.svg
| ImageSize      = 150px
| ImageAlt       = <!-- Names -->
| IUPACName= 1,1,1-Trimethyl-''N'',''N''-bis(trimethylsilyl)silanamine
| OtherNames     = 九甲基三硅氮烷
<!-- Sections -->
| Section1       = {{Chembox Identifiers
| CASNo = 1586-73-8
| CASNo_Ref = {{cascite|correct|CAS}}
| PubChem = 74110
|  EINECS = 216-445-0
|  ChemSpiderID = 66724
|  SMILES = C[Si](C)(C)N([Si](C)(C)C)[Si](C)(C)C
|  StdInChI = 1S/C9H27NSi3/c1-11(2,3)10(12(4,5)6)13(7,8)9/h1-9H3
|  StdInChIKey = PEGHITPVRNZWSI-UHFFFAOYSA-N
  }}
| Section2       = {{Chembox Properties
| Formula = C<sub>9</sub>H<sub>27</sub>NSi<sub>3</sub>
| MolarMass = 233.57
| Appearance = 蜡状固体
| Density = 
| MeltingPt = 67–69ºC
| BoilingPt = 215ºC（85ºC当13mmHg）
| SolubleOther = 易溶于非极性溶剂如：[[苯]]、[[四氯甲烷]]、[[乙醚]]、[[1,4-二氧六环]]、[[石油醚]]<ref name="Goubeau" />和[[四氢呋喃]]<ref name="Lehn" />
  }}
| Section3       = {{Chembox Hazards
| MainHazards =
| FlashPt =
| AutoignitionPt =
  }}
| Section4       = 
| Section5       = 
| Section6       = 
}}

'''三(三甲基硅基)胺'''是[[氨]]的所有氢原子都被[[三甲基硅基]] (-Si(CH<sub>3</sub>)<sub>3</sub>)取代而成的化合物。<ref name="Goubeau" >{{citation|surname1=J. Goubeau, J. Jiminéz-Barberá|periodical=[[ZAAC]]|title=Tris-(trimethylsilyl)-amin|volume=303|issue=5–6|pages=217–226|date=  1960|language=de|doi=10.1002/zaac.19603030502}}</ref>三(三甲基硅基)胺在多年来一直都是研究热点，因为它可作为化学[[固氮]]（在[[标准情况]]下把[[氮气]] N<sub>2</sub>转化成有机化合物）的稳定中间体。<ref name="Shiina" >{{citation|surname1=K. Shiina|periodical=[[J. Am. Chem. Soc.]]|title=Reductive silylation of molecular nitrogen via fixation to tris(trimethylsilyl)amine|volume=94|issue=26|pages=9266–9267|date=  1972|doi=10.1021/ja00781a068}}</ref><ref name="MacLeod" >{{citation|surname1=K.C. MacLeod, P.L. Holland|periodical=Nature Chemistry|title=Recent developments in the homogeneous reduction of dinitrogen by molybdenum and iron|volume=5|pages=559–565|date=  2013|doi=10.1038/nchem.1620|pmc=3868624|pmid=23787744}}</ref><ref>{{citation|surname1=W.I. Dzik|periodical=Inorganics|title=Silylation of dinitrogen catalyzed by hydridodinitrogen(triphenylphosphine) cobalt (I)|volume=4|issue=3|pages=21|date=  2016|doi=10.3390/inorganics4030021|doi-access=free}}</ref>

== 制备==
早期尝试制备三(三甲基硅基)胺的方法是[[三甲基氯硅烷]]和氨的反应，但即便再500&nbsp;°C的高温下，反应也未能成功。<ref>{{citation|surname1=R.O. Sauer|periodical=[[J. Am. Chem. Soc.]]|title=Derivatives of the methylchlorosilanes. I. Trimethylsilanol and its simple ethers|volume=66|issue=10|pages=1707–1710|date=  1944|doi=10.1021/ja01238a030}}</ref><ref>{{citation|surname1=R.O. Sauer, R.H. Hasek|periodical=[[J. Am. Chem. Soc.]]|title=Derivatives of the methylchlorosilanes. IV. Amines|volume=68|issue=2|pages=241–244|date=  1946|doi=10.1021/ja01206a028}}</ref>这个反应在[[双(三甲基硅基)胺]]时就停止了。

[[File:HMDS-Synthese.svg|250px|center|Synthese von Hexamethyldisilazan (HMDS)]]

三(三甲基硅基)胺是从二(三甲基硅基)胺的钠盐制备的，后者则是二(三甲基硅基)胺和[[氨基钠]]<ref name="InorgSynth1" />或是二(三甲基硅基)胺、[[钠]]和[[苯乙烯]]反应而成的。<ref name="Goubeau" />这种钠盐和三甲基氯硅烷反应可得到三(三甲基硅基)胺，[[产率]] 80%。<ref name="Wannagat" >{{citation|surname1=U. Wannagat, H. Niederprüm|periodical=[[Chem. Ber.]]|title=Beiträge zur Chemie der Silicium-Stickstoff-Verbindungen, XIII. Silylsubstituierte Alkaliamide|volume=94|issue=6|pages=1540–1547|date=  1961|language=de|doi=10.1002/cber.19610940618}}</ref>
:<math chem>\begin{matrix}{}\\
\ce{[(CH3)3Si]2NH ->[+\ce{NaNH2}][-\ce{NH3}] NaN[Si(CH3)3]2 ->[+\ce{ClSi(CH3)3}][-\ce{NaCl}] N[Si(CH3)3]3}\\
{}\end{matrix}</math>

二(三甲基硅基)胺的锂盐（可由二(三甲基硅基)胺和[[丁基锂]]<ref name="InorgSynth2" >{{citation|surname1=E.H. Amonoo-Neizer, R.A. Shaw, D.O. Skovlin, B.C. Smith, J.W. Rosenthal, W.L. Jolly|editor-surname1=H.F. Holtzlow|title=Lithium Bis(trimethylsilyl)amide and Tris(trimethylsilyl)amine, in Inorganic Syntheses|volume=8|publisher=John Wiley & Sons, Inc.|publication-place=Hoboken, NJ, USA|pages=19–22|isbn=9780470131671|date=  1966|doi=10.1002/9780470132395.ch5}}</ref>或[[苯基锂]]<ref name="Wannagat" />反应而成）和三甲基氯硅烷的反应，产生三(三甲基硅基)胺的产率为 50-60%。

氮化锂和三甲基氯硅烷在 THF 的一锅法反应的产率为 72%。<ref name="Lehn" >{{citation|surname1=W.L. Lehn|periodical=[[J. Am. Chem. Soc.]]|title=Preparation of tris(trimethylsilyl)- and tris(trimethylstannyl)amines|volume=86|issue=2|pages=305|date=  1964|doi=10.1021/ja01056a057}}</ref>
:<chem>Li3N + 3Me3SiCl -> N(Me3Si)3 + 3LiCl</chem>

== 性质==
三(三甲基硅基)胺是一种无色晶体<ref name="Sigma" >{{Sigma-Aldrich|Aldrich|id=360120|Name= Tris(trimethylsilyl)amine 98% |accessdate =28. Dezember 2016}}</ref><ref name="Alfa">{{Alfa|L04361|Name=Nonamethyltrisilazane| Datum=28. Dezember 2016}}</ref>或蜡状固体，<ref name="InorgSynth1" >{{citation|surname1=C.R. Krüger, H. Niederprüm, M. Schmidt, O. Scherer|editor-surname1=H.F. Holtzlow|title=Sodium Bis(trimethylsilyl)amide and Tris(trimethylsilyl)amine, in Inorganic Syntheses|volume=8|publisher=John Wiley & Sons, Inc.|publication-place=Hoboken, NJ, USA|pages=15–19|isbn=9780470131671|date=  1966|doi=10.1002/9780470132395.ch5}}</ref>对水和键稳定。<ref>{{citation|surname1=U. Wannagat, H. Niederprüm|periodical=[[ZAAC]]|title=dreifach silylierte Amine|volume=308|issue=1–6|pages=337–351|date=  1961|language=de|doi=10.1002/zaac.19613080135}}</ref>醇和酸会断裂Si-N键，放出氨。<ref name="InorgSynth1" />

== 应用==
===  作为合成结构单元 ===
三(三甲基硅基)胺和[[三氯化锑]]反应，几乎可以在-60 °C下形成氮化锑{{le|类立方烷簇合物|cubane-type cluster}}。<ref>{{citation|surname1=M. Rhiel, F. Weller, J. Pebler, K. Dehnicke|periodical=[[Angew. Chem.]]|title=[SbN(SbCl)<sub>3</sub>(NSbCl<sub>2</sub>)(NSiMe<sub>3</sub>)<sub>3</sub>·SbCl<sub>3</sub>], ein ungewöhnlicher Nitridoantimonkomplex mit Heterocubanstruktur|volume=106|issue=5|pages=599–600|date=  1994|language=de|doi=10.1002/ange.19941060519}}</ref>

在[[P4-t-Bu|P<sub>4</sub>-''t''-Bu]]和三(三甲基硅基)胺存在下，酮可以在温和条件下{{le|三氟甲基化|Trifluoromethylation}}。使用惰性的[[三氟甲烷]]（HCF<sub>3</sub>，HFC-23）三氟甲基化，产率高达84%。<ref>{{citation|surname1=S. Okusu, K. Hirano, E. Tokunaga, N. Shibata|periodical=[[ChemistryOpen]]|title=Organocatalyzed trifluormethylation of ketones and sulfonyl fluorides by fluoroform under a superbase system|volume=4|pages=581–585|date=  2015|doi=10.1002/open.201500160|pmc=4608523|pmid=26491635}}</ref>

[[单体]]三氯(三甲基硅基)磷氮烯 Cl<sub>3</sub>P=NSiMe<sub>3</sub> 可以由三(三甲基硅基)胺和[[五氯化磷]]在 0&nbsp;°C的[[己烷]]反应而成，

[[File:Synthese von Trichlor(trimethylsilyl)phosphoranimin.svg|400px|center|Synthese von Trichlor(trimethylsilyl)phosphoranimin]]

这种单体可以聚合成{{le|聚(二氯磷氮烯)|Poly(dichlorophosphazene)}}，它具有确定的分子量和{{le|分散性|Polydispersity}}。<ref>{{Cite patent|country =US |number =5698664 |Code= |title=Synthesis of polyphosphazenes with controlled molecular weight and polydispersity |V-Datum =1997-12-16 |A-Datum =1995-4-26 |Erfinder =H.R. Allcock, C.T. Morrissey, I. Manners, C.H. Honeyman  | Anmelder = The Penn State Research Foundation, University of Toronto | DB =Google}}</ref>

[[三氟化氮]] NF<sub>3</sub>（用于硅晶片的等离子蚀刻）可以由三(三甲基硅基)胺和[[氟气]]在–40&nbsp;°C 的[[乙腈]]反应而成。反应抑制了氮气和四氟肼的产生，它们是从氨或[[氟化铵]]合成三氟化氮的过程中，作为不良的副产物产生的。<ref>{{Cite patent|country =US |number =8163262 |Code=B1 |title=Method for production of nitrogen fluoride from trimethylsilylamines |V-Datum =2012-4-24 |A-Datum =2011-1-4 |Erfinder =B. A. Omotowa | Anmelder = | DB =Google}}</ref>

[[File:Bildung von Stickstofftrifluorid.svg|450px|center|Synthese von NF<sub>3</sub>]]

=== 化学固氮===
哈伯-博施法使固氮成为可能。在高温（>400°C）、高压（>150 [[bar]]）和铁催化剂存在下，氮气可以被还原[[质子化]]成氨。在化学固氮（即在正常条件下将大气中的氮气转化为化学合成的反应性原料，通常还有氨）中，三(三甲基硅基)胺在所谓的还原性{{le|甲硅烷基化|Silylation}}中起着重要作用，因为它的水解会产生氨。

:<math chem>\ce{ {N2} + {6e^-} ->[\ce{Catalyst:}\ \ce{Mo},\ \ce{Fe},\ \ce{Co}]}
\begin{cases}
\ce{->[\ce{H+}]} &\ce{2NH3}\\{}\\
\ce{->[\ce{R3Si-X}][-\,\ce{X-}]} &\ce{2N(SiR3)3}
\end{cases}
</math>
早在1895年，人们就发现[[锂]]在室温下就会和氮气反应，形成[[氮化锂]]。<ref>{{citation|surname1=H. Deslandres|periodical=Comptes rendus|title=Absorption de l’azote par le lithium à froid|volume=121|pages=886–887|date=1895|url=http://gallica.bnf.fr/ark:/12148/bpt6k3077p/f887.item.r=Deslandres.zoom|accessdate=2021-08-10|archive-date=2021-04-29|archive-url=https://web.archive.org/web/20210429162229/https://gallica.bnf.fr/ark:/12148/bpt6k3077p/f887.item.r=Deslandres.zoom|dead-url=no}}</ref>1972年，K. Shiina 观察到了锂（作为{{le|电子给体|electron donor}}）在三甲基氯硅烷和[[三氯化铬]]催化下和氮气反应，形成三(三甲基硅基)胺。<ref name="Shiina" />
:<math chem>\ce{N2 + 6Me3SiCl + 6}\,{\color{NavyBlue}\ce{Li}}\ \ce{->[\ce{CrCl3}] 2N(SiMe3)3 + 6}\,{\color{NavyBlue}\ce{Li}}\ce{Cl}</math>

最近发现N<sub>2</sub>的还原性甲硅烷基化反应中，可以用钠代替锂，然后用[[钼]]<ref>{{citation|surname1=Q. Liao, N. Saffon-Merceron, N. Mézailles|periodical=ACS Catal.|title=N<sub>2</sub> reduction into silylamine at tridentate phosphine/Mo center: catalysis and mechanistic study|volume=5|issue=11|pages=6902–6906|date=  2015|doi=10.1021/acscatal.5b01626}}</ref>和铁化合物<ref name="MacLeod" />（像是[[五羰基铁]]或[[二茂铁]]类<ref>{{citation|surname1=M. Yuki, H. Tanaka, K. Sasaki, Y. Miyake, K. Yoshizawa, Y. Nishibayashi|periodical=Nature Communications|title=Iron-catalyzed transformation of molecular dinitrogen into silylamine under ambient conditions|volume=3|pages=1254|date=  2012|doi=10.1038/ncomms2264|doi-access=free}}</ref>）作催化剂。催化剂中的每个铁原子可以催化高达34个 N(Me<sub>3</sub>Si)<sub>3</sub>分子。

:<math chem>\ce{N2 + 6Me3SiCl + 6}\,{\color{Red}\ce{Na}}\ \ce{->[\ce{Fe-catalyst}] 2N(SiMe3)3 + 6}\,{\color{Red}\ce{Na}}\ce{Cl}</math> 
使用钼-二茂铁配合物作为催化剂，{{le|翻转数|turnover number}}可高达 226。<ref>{{citation|surname1=H. Tanaka|display-authors=etal|periodical=[[J. Am. Chem. Soc.]]|title=Molybdenum-Catalyzed Transformation of Molecular Dinitrogen into Silylamine: Experimental and DFT Study on the Remarkable Role of Ferrocenyldiphosphine Ligands|volume=133|issue=10|pages=3498–3506|date=  2011|doi=10.1021/ja109181n}}</ref>

:<math chem>{\color{Red}\ce{N2}} + {\color{NavyBlue}\ce{Me3Si}}\ce{{Cl} + Na ->[\ce{Mo/Fe-catalyst}.][\ce{RT}\atop (1\ \ce{atm})]}\ 
{\color{Red}\ce{N}}{\color{NavyBlue}\ce{(Me3Si)3}}</math>
尽管进行了深入的研究，<ref>{{citation|surname1=Y. Nishibayashi|periodical=[[Inorg. Chem.]]|title=Recent progress in transition-metal-catalyzed reduction of molecular dinitrogen under ambient reaction conditions|volume=54|issue=19|pages=9234–9247|date=  2015|doi=10.1021/acs.inorgchem.5b00881}}</ref>迄今为止开发的化学固氮催化剂的催化生产率仍比现代的茂金属型聚合催化剂或[[酶]]小。 

== 参考资料==
{{Reflist}}

[[Category:负三价氮化合物]]
[[Category:三甲基硅基化合物]]