- Catalytic Hydrosilylation of Hydrofluoroolefins (HFOs): Synthesis of New Fluorinated Silanes and Diversity of their Synthetic Character
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New polyfluorinated silanes were synthesized via the Pt, Rh and Pd catalyzed hydrosilylation of commercially available hydrofluoroolefins (HFOs) in moderate to excellent yields. HFO-1234yf (2,3,3,3-tetrafluoropropene-1) and –1234ze (1,3,3,3-tetrafluoropropene-1) were reactive with Pt catalyst to form tetrafluoropropylsilanes along with defluorosilylation products. The Z- and E-isomers of HFO-1336mzz (1,1,1,4,4,4-hexafluorobut-2-ene) gave the desired silanes with Pd catalysis in good to excellent yields, while with Pt catalyst only the dehydrofluorination product CF2=CHCH2CF3 (HFO-1345czf, 1,1,4,4,4-pentafluorobut-1-ene) was obtained. Synthetic applications of the new polyfluorinated silanes were illustrated by conversion of dichloro(hexafluorobutyl)(methyl)silane to the cyclic trisiloxane, which can serve as a monomer for the preparation of polysiloxanes. In addition, the hexafluorobutylsilanes showed defluorinative reactivity with lithium reagents, thereby demonstrating their synthetic utility as valuable building blocks for further transformations via C–F and C-Si bond activation.
- Pavlenko, Natalia V.,Peng, Sheng,Petrov, Viacheslav,Jackson, Andrew,Sun, Xuehui,Sprague, Lee,Yagupolskii, Yurii L.
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p. 5425 - 5435
(2020/08/14)
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- The hydrosilylation of propylene
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The reactions of separate and competitive hydrosilylation of propylene with HSiCl3, MeSiHCl2, Me2SiHCl, and MePh2SiH in the presence of the Speier catalyst (SC) with different additives and a catalyst obtained from SC and propylene were studied. A mutual influence of the hydrosilanes in the competitive reactions was found. The influence of various additives to SC on the process was considered.
- Chernyshev,Belyakova,Yagodina,Nikitinskii,Bykovchenko
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p. 1992 - 1995
(2007/10/03)
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- Redistribution of dichlorosilanes and dihydridosilanes. Synthesis of chloro hydridosilanes
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The redistribution of dichlorosilanes RSi(CH3)Cl2 and dihydridosilanes RSi(CH3)H2, prepared by reduction of the homologues dichlorosilanes, in the presence of a quaternary ammonium salt is presented. The influence of the nature of R (fluoroalkyl chain RFCH2CH2 with RF = CF3, C4F9, C8F17, alkyl chain R = C6H13 or aromatic R = C6H5) and of the temperature on the rate of the reaction is studied. The equilibrium constants and free enthalpies are calculated and discussed taking into account the nature of R. The new products described were characterized from I.R, 1H, 19F and 29Si NMR spectroscopies.
- Benouargha,Boulahia,Boutevin,Caporiccio,Guida-Pietrasanta,Ratsimihety
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- THE REACTIONS OF HYDROSILANES WITH TRIFLUOROPROPENE AND PENTAFLUOROSTYRENE CATALYZED BY RUTHENIUM, RHODIUM AND PALLADIUM COMPLEXES
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The reactions of hydrosilanes with trifluoropropene (TFP) and pentafluorostyrene (PFS) catalyzed by Ru3(CO)12 or RhCl(PPh3)3 give β-Rf-vinylsilane (1) and/or β-Rf-ethylsilane (2) (Rf=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-Rf-vinylsilane nor α-Rf-ethylsilane was formed at all.Possible mechanisms which can accommodate characteristic features of these reactions are discussed.The hydrosilylation of TFP with dichloromethylsilane catalyzed by PdCl2(PhCN)2/2PPh3 gives the α-adduct (9a) exclusively, and this is transformed to the corresponding dialkoxysilanes, silane diol, oligosilane diols and cyclic oligosiloxanes.
- Ojima, Iwao,Fuchikami, Takamasa,Yatabe, Momoko
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p. 335 - 346
(2007/10/02)
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