268:
60:
94:, wherein the Si-H bond is not fully broken. Variations of the Chalk-Harrod mechanism exist. Some cases involve insertion of alkene into M-Si bond followed by reductive elimination, the opposite of the sequence in the Chalk-Harrod mechanism. In certain cases, hydrosilylation results in vinyl or allylic silanes resulting from
258:
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. The resulting monolayer, which is stable and inert, inhibits oxidation of the base silicon layer, relevant to
334:
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".
610:"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.
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was later introduced. It is a lipophilic complex that is soluble in the organic substrates of industrial interest. Complexes and compounds that catalyze hydrogenation are often effective catalysts for hydrosilylation, e.g.
275:
Before introduction of platinum catalysts by Speier, hydrosilylation was not practiced widely. A peroxide-catalyzed process was reported in academic literature in 1947, but the introduction of Speier's catalyst
568:
Applied homogeneous catalysis with organometallic compounds : a comprehensive handbook : applications, developments. Boy
Cornils; W A Herrmann. Publisher: Weinheim ; New York : Wiley-VCH,
601:"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).
503:
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)
211:. 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:
368:
Troegel, D.; Stohrer, J. (2011). "Recent
Advances and Actual Challenges in Late Transition Metal Catalyzed Hydrosilylation of Olefins from an Industrial Point of View".
604:"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).
494:"Photoreactivity of Unsaturated Compounds with Hydrogen-Terminated Silicon (111)," R. L. Cicero, M. R. Linford, C. E. D. Chidsey, Langmuir 16, 5688-5695 (2000)
607:"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.
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548:
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317:"Hydrosilylation A Comprehensive Review on Recent Advances" B. Marciniec (ed.), Advances in Silicon Science, Springer Science, 2009.
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Hayashi, T.; Yamasaki, K. (2007). "C–E Bond
Formation through Asymmetric Hydrosilylation of Alkenes". In Crabtree, Robert H.;
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give silyl ethers. Hydrosilylation has been called the "most important application of platinum in homogeneous catalysis."
575:
Rhodium complexes as hydrosilylation catalysts. N.K. Skvortsov. // Rhodium
Express. 1994. No 4 (May). P. 3 - 36 (Eng).
153:, catalysts have been developed for catalytic asymmetric hydrosilation. A well studied reaction is the addition of
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628:
95:
513:
Sommer, L.; Pietrusza, E.; Whitmore, F. (1947). "Peroxide-catalyzed addition of trichlorosilane to 1-octene".
572:
Comprehensive handbook on hydrosilylation. Bogdan
Marciniec. Publisher: Oxford : Pergamon Press, 1992.
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27:. Ordinarily the reaction is conducted catalytically and usually the substrates are unsaturated
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of alkenes. In fact, similar catalysts are sometimes employed for the two catalytic processes.
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Si), and the alkene substrate. Oxidative addition proceeds by the intermediacy of a
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Hydrosilylation of alkenes represents a commercially important method for preparing
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James L. Fry, Ronald J. Rahaim Jr., Robert E. Maleczka, Jr. "Triethylsilane",
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397:"Markovnikov Hydrosilylation of Alkenes: How an Oddity Becomes the Goal"
105:, i.e., silicon is placed at the terminal carbon when hydrosilylating a
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Idealized mechanism for metal-catalysed hydrosilylation of an alkene.
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Alkynes also undergo hydrosilylation, e.g., the addition of
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supported by binaphthyl-substituted monophosphine ligands.
82:, assumes an intermediate metal complex that contains a
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Kartstedt's catalyst is often used in hydrosilylation.
101:Hydrosilylation of alkenes usually proceeds via
71:. The process is mechanistically similar to the
435:Encyclopedia of Reagents for Organic Synthesis
337:Ullmann's Encyclopedia of Industrial Chemistry
23:, describes the addition of Si-H bonds across
395:Zaranek, Maciej; Pawluc, Piotr (2018-10-05).
8:
313:
311:
207:(HF) to remove the native oxide and form a
161:to give 1-phenyl-1-(trichlorosilyl)ethane:
464:Comprehensive Organometallic Chemistry III
113:has become a growing field of research.
58:
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543:(2006) Wiley and Sons-VCH: Weinheim.
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78:The prevalent mechanism, called the
209:hydrogen-terminated silicon surface
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109:; however, in the recent years,
472:10.1016/B0-08-045047-4/00140-0
1:
447:10.1002/047084289X.rt226.pub2
259:various device applications.
188:(ee's) can be achieved using
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287:) was a big breakthrough.
141:Asymmetric hydrosilylation
382:10.1016/j.ccr.2010.12.025
323:10.1007/978-1-4020-8172-9
103:anti-Markovnikov addition
413:10.1021/acscatal.8b03104
345:10.1002/14356007.a21_075
149:phosphines as spectator
96:beta-hydride elimination
466:. Amsterdam: Elsevier.
196:Surface hydrosilylation
132:SiH + PhC≡CPh → Et
69:organosilicon compounds
21:catalytic hydrosilation
272:
80:Chalk-Harrod mechanism
64:
439:John Wiley & Sons
270:
62:
460:D. Michael P. Mingos
376:(13–14): 1440–1459.
296:Wilkinson's catalyst
186:enantioselectivities
111:Markovnikov addition
527:10.1021/ja01193a508
291:Karstedt's catalyst
190:palladium catalysts
86:, a silyl ligand (R
55:Scope and mechanism
581:2022-06-23 at the
539:C. Elschenbroich,
273:
65:
549:978-3-527-29390-2
481:978-0-08-045047-6
407:(10): 9865–9876.
205:hydrofluoric acid
203:can be etched in
122:diphenylacetylene
29:organic compounds
25:unsaturated bonds
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521:(1): 188.
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302:References
590:0869-7876
421:2155-5435
339:. Wiley.
263:Catalysts
173:→ (Ph)(CH
45:aldehydes
596:Articles
579:Archived
462:(eds.).
441:, 2007.
624:Silicon
235:→ Si-CH
223:C=CH(CH
177:)CHSiCl
159:styrene
151:ligands
84:hydride
49:ketones
37:alkynes
33:Alkenes
588:
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147:chiral
145:Using
569:2000.
563:Books
586:ISSN
545:ISBN
476:ISBN
417:ISSN
349:ISBN
282:PtCl
243:-(CH
47:and
35:and
523:doi
468:doi
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378:doi
374:255
341:doi
319:doi
219:+ H
215:Si-
157:to
120:to
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519:69
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310:^
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251:CH
239:CH
231:CH
165:Cl
128:Et
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280:2
278:H
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253:3
249:7
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241:H
237:2
233:3
229:7
227:)
225:2
221:2
217:H
179:3
175:3
171:2
167:3
134:3
130:3
88:3
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