Reactions Of Hydrosilanes Research Articles

Palladium‐Catalyzed Dehydrogenation Cross‐Coupling Reactions of Hydrosilanes: Facile Synthesis of Silanols and Silyl Ethers

AbstractA palladium‐catalyzed dehydrogenative cross‐coupling reactions between silanes and oxygen‐containing functional groups (water, alcohols, phenols) to generate the corresponding silanols, monosilane ethers, and disilane ethers directly in moderate to high yields. This strategy does not rely on any additional oxidizing agents or proton reductants. The possible mechanisms for this transformation are also proposed.

ChemInform Abstract: Reactions of Hydrosilanes with Transition Metal Complexes and Characterization of the Products

AbstractReview: 830 refs.

Reactions of Hydrosilanes with Transition Metal Complexes and Characterization of the Products

Reactions of Hydrosilanes with Transition Metal Complexes and Characterization of the Products

The Solvent Effects on Kinetics and Mechanism of Zinc or Cadmium Halide Catalyzed Reactions of Hydrosilanes with Hydroxylic Reagents

The effect of solvent composition on reaction rates was studied by a kinetic method for reactions of Et3SiH with Ph2Si(OH)2 in the presence of ZnCl2 in a mixture of DMF and THF or Et3SiH with PhCOOH and cadmium bromide CdBr2 in DMF-1,4-dioxane and DMF-THF. A decrease in reaction rates with decreasing polarity of the medium (and its dielectric constant) has been observed. The kinetic order of dehydrocoupling reaction with respect to DMF was determined from kinetic studies. The constants of nucleophilic catalysis with DMF (λ) were found. The role of DMF in the mechanism of dehydrocoupling of hydrosilanes with hydroxylic reagents in the presence of ZnX2 and CdX2 halides (X = Cl, Br, I) is discussed.

ChemInform Abstract: Synthesis of Bromohydrosilanes: Reactions of Hydrosilanes with CuBr2 in the Presence of CuI.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis of Bromohydrosilanes: Reactions of Hydrosilanes with CuBr2 in the Presence of CuI

Abstract Reactions of hydrosilanes, R4−nSiHn (R = alkyl or phenyl, n = 1–3), with 2 equiv of CuBr2 in the presence of a catalytic amount of CuI led to selective replacement of an H–Si bond with a Br–Si bond giving R3SiBr, R2SiHBr, or RSiH2Br, while treatment of R2SiH2 and RSiH3 with 4 equiv of the reagent produced R2SiBr2 and RSiHBr2, respectively. Similar reaction of Het2SiSiEt2H afforded Het2SiSiEt2Br.

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds.

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds.

The reactions of hydrosilanes with the methoxycarbonyl complexes Cp(L)(CO)MCO 2Me(MFe, Ru; LCO,PPh 3) and (L)(CO) xMCO 2Me(MCo, Mn; LCO, PPh3; x = 3,4, with and without catalysis

The reactivity of selected organotransition metal methoxycarbonyl complexes towards hydrosilanes differs significantly from their acetyl analogs in that hydrosilation does not occur across the methoxycarbonyl ligand. Only hydrosilane/manganese carbonyl precatalyst systems that had proved to be more active towards the acetyl ligand on Cp(L)(CO)MC(O)CH 3 (MFe, Ru; LCO,PPh 3, PPh 3) reacted with the methoxycarbonyl complexes Cp(CO) 2MCO 2CH 3 ( 1, MFe; 2, MRu). These reactions involving PhSiH 3/2–3% (PPh 3)(CO) 4MnC(O)CH 3 for 1 and 2, or PhMe 2SiH/2–3% (CO) 5MnCH 3 for 1 afforded their η 4-cyclopentadiene compounds ( η 4-C 5H 6)M(CO) 3 (MFe,Ru) plus methoxysilanes. Results with PhMe 2SiD/3% (CO) 5MnCH 3 support exo deuteride transfer to the Cp ligand; a mechanism is proposed. The low reactivity of methoxycarbonyl complexes under hydrosilation catalysis conditions also is consistent with the inactivity of PhSiH 3 or Ph 2SiH 2/Rh(PPh 3) 3Cl towards 1 or 2 and with the inertness of Cp(PPh 3)(CO)FeCO 2CH 3 and Cp ∗(CO) 2FeCO 2CH 3 under all attempted hydrosilation conditions. This diminution of hydrosilane reactivity extends to cobalt and manganese carbonyl methoxycarbonyl complexes (L)(CO) x MCO 2CH 3 ( 3, MMn, x = 4, LCO; 4, MCo, x = 3, LPPh 3; 5, MCo, x = 3, LCO). Although their acetyl analogs (L)(CO) x MC(O)CH 3 are sensitive to hydrosilanes, both 3 and 4 are inert towards PhMe 2SiH or Ph 2SiH 2. Treatment of 5 with PhMe 2SiH released methyl formate and left the silyl complex (CO) 4CoSiMe 2Ph, a result that resembles the hydrogenation chemistry of 5.

Silylformylation catalyzed by Rh and Rh-Co mixed metal complexes and its application to the synthesis of pyrrolizidine alkaloids

Reactions of hydrosilanes with 1-hexyne catalyzed by Co 2Rh 2(CO) 12, Rh 4(CO) 12, ( tBuNC) 4RhCo(CO) 4, and Rh(acac)(CO) 2 at 25°C and atmospheric pressure to 10 atm of carbon monoxide give (Z)-1-silyl-2-formyl-1-hexenes ( 1), which are the products of “silylformylation”, and/or ( E)-1-silyl-1-hexenes ( 2). The ratio of silylformylation vs. hydrosilylation products depends on the electronic nature of hydrosilane used, e.g., PhMe 2SiH gives 1 almost exclusively whereas (MeO) 3SiH favors the formation of 2. When trialkylsilanes such as Et 3SiH and EtMe 2SiH are used, the reaction catalyzed by Co 2Rh 2(CO) 12 or ( tBuNC) 4RhCo(CO) 4 gives 2,5-bis(n-butyl)-3-silylcyclopent-2-en-1-one ( 3) as a major product, which is a unique silylcarbocyclization product. Mechanism of the formation of 3 is discussed on the basis of deuterium-labeling experiments. Chemoselective silylformylations of alkenynes, a dialkyne, and an alkynyl nitrile proceed in high yields in which alkene and nitrile functionalities are inert for the reaction. Silylformylation is successfully applied to the syntheses of pyrrolizidine alkaloids, (±)-isoretronecanol and (±)-trachelanthamidine, from 5-ethynyl-2-pyrrolidinone ( 6) in combination with amidocarbonylation.

ChemInform Abstract: Platinum‐Mediated Reactions of Hydrosilanes. Isolation of a Complex with Bridging Disilene and Silylene Ligands.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reactions of hydrosilanes and olefins in the presence of Cp2MCl2/BuLi

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactions of hydrosilanes and olefins in the presence of Cp2MCl2/BuLiJoyce Y. Corey and Xiao Hong ZhuCite this: Organometallics 1992, 11, 2, 672–683Publication Date (Print):February 1, 1992Publication History Published online1 May 2002Published inissue 1 February 1992https://doi.org/10.1021/om00038a027RIGHTS & PERMISSIONSArticle Views475Altmetric-Citations84LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (2 MB) Get e-Alerts Get e-Alerts

Silylformylation of 1-hexyne catalyzed by rhodium-cobalt mixed-metal carbonyl clusters

Reactions of hydrosilanes with 1-hexyne catalyzed by Co 2 Rh 2 (CO) 12 and Rh 4 (CO) 12 at 25 o C and atmospheric pressure-150 psi of carbon monoxide give (Z)-1-silyl-2-formyl-1-hexenes, which are the products of «silylformylation», and/or (E)-1-silyl-1-hexenes

The reactions of hydrosilanes with trifluoropropene and pentafluorostyrene catalyzed by ruthenium, rhodium and palladium complexes

The reactions of hydrosilanes with trifluoropropene (TFP) and pentafluorostyrene (PFS) catalyzed by Ru 3(CO) 12 or RhCl(PPh 3) 3 give β-R f-vinylsilane ( 1) and/or β-R f-ethylsilane ( 2) (R f = perfluorocarbon group). The 1/2 ratio is highly dependent on the nature of hydrosilane used. The ruthenium catalyst favors the formation of 1 compared with the rhodium catalyst. Neither α-R f-vinylsilane nor α-R f-ethyl-silane was formed at all. Possible mechanisms which can accommodate characteristic features of these reactions are discussed. The hydrosilylation of TFP with dichloro-methylsilane catalyzed by PdCl 2(PhCN) 2/2PPh 3 gives the α-adduct ( 9a) exclusively, and this is transformed to the corresponding dialkoxysilanes, silane diol, oligosilane diols and cyclic oligosiloxanes.

Addition reactions of hydrosilanes to enyne systems

1. A study was made of the reaction of trialkylsilanes with ethynylvinyl ethers, amines, and sulfides. 2. With the exception of the sulfides, the addition of the trialkylsilanes under the influence of H2PtCl6 takes place at the triple bond with the formation of the corresponding organosilicon diene compounds.