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Hydrosilylation, also called catalytic hydrosilation, describes the addition of Si-H bonds across unsaturated bonds.[1] Ordinarily the reaction is conducted catalytically and usually the substrates are unsaturated organic compounds. Alkenes and alkynes give alkyl and vinyl silanes; aldehydes and ketones give silyl ethers. Hydrosilylation has been called the "most important application of platinum in homogeneous catalysis."[2] The process was first reported in academic literature in 1972.[3]
Contents
- 1 Scope and mechanism
- 2 Asymmetric hydrosilylation
- 3 Surface hydrosilylation
- 4 References
- 5 Further reading
- 5.1 Additional specialized literature
Scope and mechanism[edit source | edit]
The catalytic transformation represents an important method for preparing organosilicon compounds. An idealized transformation is illustrated by the addition of triethylsilane to diphenylacetylene:[4]
- Et3SiH + PhC≡CPh → Et3Si(Ph)C=CH(Ph)
The reaction is related mechanistically to hydrogenation, and similar catalysts are sometimes employed for the two catalytic processes. Popular industrial catalysts are "Speier's catalyst," H2PtCl6, and Karstedt’s catalyst (an alkene-stabilized platinum(0) catalyst.[5] The mechanism, called the Chalk-Harrod mechanism, assumes an intermediate metal complex that contains a hydride, a silyl ligand (R3Si), and the alkene or alkyne substrate. The products usually involve anti-Markovnikov addition.[1]
Idealized mechanism for metal-catalysed hydrosilylation of an alkene.
These reactions can also be catalyzed using nanomaterial-based catalysts.
Asymmetric hydrosilylation[edit source | edit]
Using chiral phosphines as spectator ligands, catalysts have been developed for catalytic asymmetric hydrosilation. A well studied reaction is the addition of trichlorosilane to styrene to give 1-phenyl-1-(trichlorosilyl)ethane:
- Cl3SiH + PhCHCH2 → (Ph)(CH3)CHSiCl3
Nearly perfect enantioselectivities (ee's) can be achieved using palladium catalysts supported by binaphthyl-substituted monophosphine ligands.[6]
Surface hydrosilylation[edit source | edit]
Silicon wafers can be etched in hydrofluoric acid (HF) to remove the native oxide and form a hydrogen-terminated silicon surface. The hydrogen-terminated surfaces undergo hydrosilation with unsaturated compounds (such as terminal alkenes and alkynes), to form a stable monolayer on the surface. For example:
- Si-H + H2C=CH(CH2)7CH3 → Si-CH2CHH-(CH2)7CH3
The hydrosilylation reaction can be initiated with UV light at room temperature or with heat (typical reaction temperature 120-200 °C), under moisture- and oxygen-free conditions.[7] The resulting monolayer, which is stable and inert, inhibits oxidation of the base silicon layer, relevant to various device applications.[8]
References[edit source | edit]
- ^ a b "Hydrosilylation A Comprehensive Review on Recent Advances" B. Marciniec (ed.), Advances in Silicon Science, Springer Science, 2009. doi:10.1007/978-1-4020-8172-9
- ^ Renner, H.; Schlamp, G.; Kleinwächter, I.; Drost, E.; Lüschow, H. M.; Tews, P.; Panster, P.; Diehl, M.; Lang, J.; Kreuzer, T.; Knödler, A.; Starz, K. A.; Dermann, K.; Rothaut, J.; Drieselman, R. (2002). "Platinum group metals and compounds". Ullmann's Encyclopedia of Industrial Chemistry. Wiley. doi:10.1002/14356007.a21_075.
- ^ Ojima, I.; Nihonyanagi, M.; Nagai, Y. "Rhodium Complex Catalysed Hydrosilylation of Carbonyl Compounds" J. Chem. Soc., Chem. Commun. 1972, 938a. doi:10.1039/C3972000938A
- ^ James L. Fry, Ronald J. Rahaim Jr., Robert E. Maleczka Jr. "Triethylsilane", Encyclopedia of Reagents for Organic Synthesis, John Wiley & Sons, 2007. doi:10.1002/047084289X.rt226.pub2
- ^ C. Elschenbroich, Organometallics (2006) Wiley and Sons-VCH: Weinheim. ISBN 978-3-527-29390-2
- ^ Hayashi, T.; Yamasaki, K. (2007). "C–E Bond Formation through Asymmetric Hydrosilylation of Alkenes". In Crabtree, Robert H.; Mingos, D. Michael P. Comprehensive Organometallic Chemistry III. Amsterdam: Elsevier. doi:10.1016/B0-08-045047-4/00140-0. ISBN 978-0-08-045047-6.
- ^ "Photoreactivity of Unsaturated Compounds with Hydrogen-Terminated Silicon (111)," R. L. Cicero, M. R. Linford, C. E. D. Chidsey, Langmuir 16, 5688-5695 (2000).
- ^ "Direct electrical detection of DNA Hybridization at DNA-modified silicon surfaces," W.Cai, J. Peck, D. van der Weide, and R.J. Hamers, Biosensors and Bioelectronics 19, 1013-1019 (2004).
Further reading[edit source | edit]
- Applied homogeneous catalysis with organometallic compounds : a comprehensive handbook : applications, developments. Boy Cornils; W A Herrmann. Publisher: Weinheim ; New York : Wiley-VCH, ©2000.
- Comprehensive handbook on hydrosilylation. Bogdan Marciniec. Publisher: Oxford [u.a.] : Pergamon Press, 1992.
- Rhodium complexes as hydrosilylation catalysts. N.K. Skvortsov. // Rhodium Express. 1994. No 4 (May). P. 3 - 36 (Eng). ISSN 0869 - 7876
Additional specialized literature[edit source | edit]
- "Alkyl Monolayers on Silicon Prepared from 1-Alkenes and Hydrogen-Terminated Silicon," M. R. Linford, P. Fenter, P. M. Eisenberger and C. E. D. Chidsey, J. Am. Chem. Soc. 117, 3145-3155 (1995).
- "Synthesis and characterization of DNA-modified Si(111) Surfaces," T. Strother, W. CAi, X. Zhao, R.J. Hamers, and L.M. Smith, J. Am. Chem. Soc. 122, 1205-1209 (2000).
- "T. Strother, R.J. Hamers, and L.M. Smith, "Surface Chemistry of DNA Covalent Attachment to the Silicon(100) Surface". Langmuir, 2002, 18, 788-796.
- "Covalently Modified Silicon and Diamond Surfaces: Resistance to Non-Specific Protein Adsorption and Optimization for Biosensing," T.L. Lasseter, B.H. Clare, N.L. Abbott, and R.J. Hamers. J. Am. Chem. Soc. 2004, 126, 10220-10221.
English Journal
- Surface chemistry of porous silicon and implications for drug encapsulation and delivery applications.
- Jarvis KL, Barnes TJ, Prestidge CA.AbstractPorous silicon (pSi) has a number of unique properties that appoint it as a potential drug delivery vehicle; high loading capacity, controllable surface chemistry and structure, and controlled release properties. The native Si(y)SiH(x) terminated pSi surface is highly reactive and prone to spontaneous oxidation. Surface modification is used to stabilize the pSi surface but also to produce surfaces with desired drug delivery behavior, typically via oxidation, hydrosilylation or thermal carbonization. A number of advanced characterization techniques have been used to analyze pSi surface chemistry, including X-ray photoelectron spectroscopy and time of flight secondary ion mass spectrometry. Surface modification not only stabilizes the pSi surface but determines its charge, wettability and dissolution properties. Manipulation of these parameters can impact drug encapsulation by altering drug-pSi interactions. pSi has shown to be a successful vehicle for the delivery of poorly soluble drugs and protein therapeutics. Surface modification influences drug pore penetration, crystallinity, loading level and dissolution rate. Surface modification of pSi shows great potential for drug delivery applications by controlling pSi-drug interactions. Controlling these interactions allows specific drug release behaviors to be engineered to aid in the delivery of previously challenging therapeutics. Within this review, different pSi modification techniques will be outlined followed by a summary of how pSi surface modification has been used to improve drug encapsulation and delivery.
- Advances in colloid and interface science.Adv Colloid Interface Sci.2012 Jul 15;175:25-38. Epub 2012 Mar 30.
- Porous silicon (pSi) has a number of unique properties that appoint it as a potential drug delivery vehicle; high loading capacity, controllable surface chemistry and structure, and controlled release properties. The native Si(y)SiH(x) terminated pSi surface is highly reactive and prone to spontaneo
- PMID 22521238
- Aryl-aryl interactions as directing motifs in the stereodivergent iron-catalyzed hydrosilylation of internal alkynes.
- Belger C, Plietker B.SourceInstitut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany. bernd.plietker@oc.uni-stuttgart.de.
- Chemical communications (Cambridge, England).Chem Commun (Camb).2012 Jun 4;48(44):5419-21. Epub 2012 Apr 26.
- The defined Fe hydride complex FeH(CO)(NO)(Ph(3)P)(2) is highly active as a catalyst for selective hydrosilylation of internal alkynes to vinylsilanes. Depending on the silane employed either E- or Z-selective hydrosilylation products were formed in excellent yields and good to excellent stereoselec
- PMID 22540131
Japanese Journal
- 光学活性ビス(オキサゾリニル)フェニル金属錯体を用いる不斉触媒反応
- 異なるシロキサン鎖長を有する脂環式テトラカルボン酸二無水物の合成とポリイミドの特性
- 菊地 宣
- 高分子論文集 = Japanese journal of polymer science and technology 70(4), 151-160, 2013
- NAID 40019713750
- Hybrid Organic-Inorganic Films through Crosslinking Reaction Based on Siloxane Based Polymers
- DEMIRCI Ali,MATSUI Jun,MITSUISHI Masaya [他]
- ネットワークポリマー = Journal of network polymer, Japan 34(1), 28-36, 2013
- NAID 40019573674
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