- Highly β(Z)-Selective Hydrosilylation of Terminal Alkynes Catalyzed by Thiolate-Bridged Dirhodium Complexes
-
A series of novel monothiolate-bridged dirhodium complexes, [Cp Rh(μ-SR)(μ-Cl)2RhCp ][BF4] {Cp? = ??5-C5Me5, R = tertiary butyl (tBu), 1a; R = ferrocenyl (Fc), 1b; R = adamantyl (Ad), 1c} were designed and successfully synthesized, which can smoothly facilitate highly regioselective and stereoselective hydrosilylation of terminal alkynes to afford β(Z) vinylsilanes with good functional group compatibility. Furthermore, the hydride bridged dirhodium complex [Cp Rh(μ-StBu)(μ-Cl)(μ-H)RhCp ][BF4] (5) as a potential intermediate was obtained by the reaction of 1a with excess HSiEt3.
- Zhao, Xiangyu,Yang, Dawei,Zhang, Yahui,Wang, Baomin,Qu, Jingping
-
supporting information
p. 5357 - 5361
(2018/09/13)
-
- The effect of an acylphosphine ligand on the rhodium-catalyzed hydrosilylation of alkenes
-
We synthesized a series of acylphosphines and investigated the hydrosilylation of alkenes that were catalyzed using RhCl3/acylphosphine. The results indicated that RhCl3/(diphenylphosphino) (phenyl)methanone exhibited higher activity as well as higher levels of β–adduct selectivity.
- Li, Jiayun,Yang, Chuang,Bai, Ying,Yang, Xiaoling,Liu, Yu,Peng, Jiajian
-
-
- Synthesis of novel poly(ethylene glycol)-containing imidazolium-functionalized phosphine ligands and their application in the hydrosilylation of olefins
-
A series of polyethylene glycol-containing imidazolium-functionalized phosphine ligands (mPEG-im-PPh2) were successfully synthesized and used in the rhodium-catalyzed hydrosilylation of olefins. The results indicate that the RhCl3/mPEG-im-PPh2 catalytic system exhibits both excellent activity and selectivity for the β-adduct. In addition, the catalytic system may be recycled at least six times.
- Zhang, Guodong,Li, Jiayun,Yang, Chuang,Niu, Congbai,Bai, Ying,Liu, Yu,Peng, Jiajian
-
-
- Effect of silylated triarylphosphine ligands on rhodium-catalyzed hydrosilylation
-
A series of silylated triarylphosphines was synthesized. Hydrosilylation reactions of styrene with triethoxysilane catalyzed by RhCl3/silylated triarylphosphine complexes were investigated. The complexes RhCl3/phenylbis(4-trimethylsilylphenyl)phosphine and RhCl3/tris(4-trimethylsilylphenyl)phosphine exhibited higher activity as well as greater β-adduct selectivity, and no unsaturated product was obtained. The results suggest that the silyl moieties have a significant impact on the catalytic process. Copyright
- Li, Jiayun,Xue, Mei,Bai, Ying,Peng, Jiajian,Xiao, Wenjun
-
p. 905 - 910
(2016/10/18)
-
- Rubber reinforcing agent, preparation method thereof, and preparation method of butadiene styrene rubber
-
The invention provides a rubber reinforcing agent, a preparation method thereof, and a preparation method of butadiene styrene rubber. In the invention, firstly the rubber reinforcing agent having excellent reaction activity with butadiene styrene rubber
- -
-
Paragraph 0052; 0053
(2016/10/10)
-
- Platinum(0) olefin complexes of a bulky terphenylphosphine ligand. Synthetic, structural and reactivity studies
-
A novel terphenylphosphine PMe2ArDipp2 (1) (Dipp = 2,6-iPr2C6H3) forms stable Pt(0) complexes with ethene and 3,3-dimethylbut-1-ene that behave as sources of the reactive Pt(PMe
- Ortega-Moreno, Laura,Peloso, Riccardo,Maya, Celia,Suárez, Andrés,Carmona, Ernesto
-
supporting information
p. 17008 - 17011
(2015/12/01)
-
- Application of polyethyleneglycol (PEG) functionalized ionic liquids for the rhodium-catalyzed hydrosilylation reaction of alkenes
-
Abstract Rh(PPh3)3Cl-polyethyleneglycol (PEG) functionalized ionic liquids with various anions were used as a catalytic system for the hydrosilylation reaction of alkenes. The influence of the anion of the ionic liquid has been investigated. It was found that the anion has an impact on the catalytic activity and selectivity. [PEG400DIL][PF6]-[Rh(PPh3)3Cl] shows an improved catalytic performance towards the hydrosilylation reaction of alkenes. The scope of alkenes and recycling of the catalytic system have been investigated.
- Bai, Ying,Zhang, Fengxiang,Li, Jiayun,Xu, Yisong,Peng, Jiajian,Xiao, Wenjun
-
-
- Combinatorial Approach to the Catalytic Hydrosilylation of Styrene Derivatives: Catalyst Systems Composed of Organoiron(0) or (II) Precursors and Isocyanides
-
(COT)2Fe and the open ferrocenes (MPDE)2Fe (MPDE = η5-3-methylpentadienyl) and (DMPDE)2Fe (DMPDE = η5-2,4-dimethylpentadienyl) were found to function as catalyst precursors for the hydrosilylation of alkenes in the presence of auxiliary ligands. Screening trials determined that the optimal catalyst system was composed of (COT)2Fe and adamantyl isocyanide, allowing the selective hydrosilylation of styrene derivatives with trisubstituted hydrosiloxanes and a polydimethylsiloxane bearing Me2SiH moieties as the end groups. Under the appropriate conditions, the dehydrogenative silylation side reaction was completely suppressed, and the reaction TON exceeded 5000. (Chemical Equation Presented).
- Sunada, Yusuke,Noda, Daisuke,Soejima, Hiroe,Tsutsumi, Hironori,Nagashima, Hideo
-
supporting information
p. 2896 - 2906
(2015/06/30)
-
- Catalysed stereodivergent hydrosilylation with Onium Salts stabilised M(0) nanocatalysts prepared in scCO2
-
M(0) nanocatalysts stabilised in Onium Salt were synthesised using an original preparation and their effectiveness in catalysing the challenging selective sterodivergent alkyne hydrosilylation reaction was studied. Four metal based nanocrystals, namely Pt
- Pascu,Liautard,Vaultier,Pucheault,Aymonier
-
p. 59953 - 59960
(2015/02/19)
-
- Hydrosilylation of alkenes catalyzed by rhodium with polyethylene glycol-based ionic liquids as ligands
-
A series of polyethylene glycol-functionalized imidazolium ionic liquids has been prepared and characterized. These ionic liquids have been successfully applied in the hydrosilylation of alkenes catalyzed by rhodium complexes. The effects of the length of the polyether chain, the amount of ionic liquid, and the reaction temperature on the catalytic performance of hydrosilylation have been investigated. Furthermore, the catalytic system has been tested for the hydrosilylation of different alkenes with triethoxysilane. The new catalytic system exhibits both excellent catalytic activity and selectivity under low-temperature conditions. The catalyst system could be recycled five times with slightly deactivation.
- Xu, Yisong,Bai, Ying,Peng, Jiajian,Li, Jiayun,Xiao, Wenjun,Lai, Guoqiao
-
-
- Catalytic study of heterobimetallic rhodium complexes derived from partially alkylated s-indacene in dehydrogenative silylation of olefins
-
This work describes the catalytic study of heterobimetallic rhodium compounds derived from partially alkylated s-indacene in dehydrogenative silylation of olefins in order to elucidate as much as possible the effects of: solvent, temperature, chemical substrates, olefin effect, silane effect, and secondary metallic fragment. The rhodium complexes, anti-[Cp*Fe-s- Ic′-Rh(COD)] 1, anti-[Cp*Ru-s-Ic′-Rh(COD)] 2, and syn-[Cp*Ru-s-Ic′-Rh(COD)] 2′ (with s-Ic′: 2,6-diethyl-4,8-dimethyl-s-indaceneiide) were previously synthesized and characterized, and were compared with the catalytic activity of the complexes previously reported; monometallic [(COD)Rh-s-Ic′H] 3, and homobimetallic anti-[{(COD)Rh}2-s-Ic′] 4, and syn-[{(COD)Rh} 2-s-Ic′] 4′. The heterobimetallic complexes show a high activity and selectivity for the dehydrogenative silylation of styrene and these complexes show also the presence of a cooperative effect between both metallic centers, which is evidenced when compared with monometallic complex.
- Adams,Riviere,Riviere-Baudet,Morales-Verdejo,Dahrouch,Morales,Castel,Delpech,Manríquez,Chávez
-
p. 266 - 274
(2013/11/19)
-
- Effect of triarylphosphane ligands on the rhodium-catalyzed hydrosilylation of alkene
-
A series of triarylphosphanes (1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a) have been synthesized. An X-ray crystal structure analysis of (2-bromophenyl)diphenylphosphane (1a) unambiguously confirmed the constitution of the functionalized phosphane. The hydrosilylation reaction of styrene with triethoxysilane catalyzed with RhCl3/triarylphosphane was studied. In comparison with the classic Wilkinson's catalyst, rhodium complexes with functionalized triarylphosphane ligands are characterized by a very high catalytic effectiveness for the hydrosilylation of alkene. Among these catalysts tested, RhCl3/diphenyl(2-(trimethylsilyl)phenyl)phosphane (8a) exhibited excellent catalytic properties. Using this silicon-containing phosphane ligand for the rhodium-catalyzed hydrosilylation of styrene, both higher conversion of alkene and higher β-adduct selectivity were obtained than with Wilkinson's catalyst.
- Xue, Mei,Li, Jiayun,Peng, Jiajian,Bai, Ying,Zhang, Guodong,Xiao, Wenjun,Lai, Guoqiao
-
p. 120 - 126
(2014/02/14)
-
- Catalytic applications of recyclable silica immobilized NHC-ruthenium complexes
-
A monosilylated Hoveyda-Grubbs ruthenium alkylidene has been prepared and grafted through the NHC ligand to a mesostructured silica, in refluxing toluene or at room temperature, giving two new organic-inorganic hybrid silica materials M2 and M3, respectiv
- Monge-Marcet, Amàlia,Pleixats, Roser,Catto?n, Xavier,Wong Chi Man, Michel
-
p. 341 - 348
(2013/01/15)
-
- Heterogeneously catalyzed aerobic cross-dehydrogenative coupling of terminal alkynes and monohydrosilanes by gold supported on oms-2
-
Cross-dehydrogenative coupling of various terminal alkynes and monohydrosilanes efficiently proceeded in the presence of gold supported on OMS-2 (Au/OMS-2) using O2 as a terminal oxidant, affording the corresponding alkynylsilanes in moderate to high yields (see picture). The observed catalysis was truly heterogeneous, and the catalyst could be reused at least ten times without a significant loss of its high catalytic performance. Copyright
- Yamaguchi, Kazuya,Wang, Ye,Oishi, Takamichi,Kuroda, Yoshiyuki,Mizuno, Noritaka
-
supporting information
p. 5627 - 5630
(2013/06/27)
-
- Further studies of fluoride ion entrapment in octasilsesquioxane cages; X-ray crystal structure studies and factors that affect their formation
-
A range of fluoride-encapsulated octasilsesquioxane cage compounds have been prepared using the TBAF route. Our studies suggest that whilst it is relatively straightforward to prepare fluoride-encapsulated octasilsesquioxane cage compounds with adjacent sp2 carbons, leading to a range of aryl and vinyl substituted compounds, the corresponding sp3 carbon derivatives are more capricious, requiring an electron withdrawing group that can stabilize the cage whilst not acting as a leaving group. Analysis by X-ray crystallography and solution 19F/29Si NMR spectroscopy of R8T8@F- reveal very similar environments for the encapsulated fluoride octasilsesquioxane cages. Migration of a fluoride ion from inside the cage to outside the cage without breaking the T8 framework and the possibility of encapsulating other anions within silsesquioxane cages have been also investigated.
- Taylor, Peter G.,Bassindale, Alan R.,El Aziz, Youssef,Pourny, Manuel,Stevenson, Richard,Hursthouse, Michael B.,Coles, Simon J.
-
experimental part
p. 2048 - 2059
(2012/04/17)
-
- Rh(pph3)3cl/tetrakis(dialkylamino)phosphonium salts as thermoregulated and recyclable catalytic system for hydrosilylation reaction
-
Eleven tetrakis(dialkylamino)phosphonium salts have been prepared and were used as "soft" catalyst supports for the hydrosilylation reaction of styrene with triethoxysilane catalyzed by Rh(PPh3)3Cl. Among the Rh(PPh3)3Cl/tetrakis(dialkylamino)phosphonium salts tested, the best catalytic activity and selectivity in favor of the β-adduct were obtained when {[(C4H9) 2N]3[(C8H17)2N]P}PF 6 was used as the support, and Rh(PPh3)3Cl/ {[(C4H9)2N]3[(C8H 17)2N]P}PF6 catalyst system can be reused more than 10 times without noticeable loss of catalytic activity and selectivity. Copyright Taylor & Francis Group, LLC.
- Wang, Diliang,Li, Jiayun,Peng, Jiajian,Bai, Ying,Lai, Guoqiao
-
experimental part
p. 2258 - 2266
(2012/03/27)
-
- Synthesis of siloxy-modified second generation Hoveyda-Grubbs catalysts and their catalytic activity
-
Efficient syntheses of the first ruthenium alkylidene complexes bearing siloxide ligands are described. Second generation Hoveyda-Grubbs catalyst is shown to undergo efficient functionalization with a number of potassium silanolates to give disiloxy deriv
- Rogalski, Szymon,Pietraszuk, Cezary,Marciniec, Bogdan
-
scheme or table
p. 3918 - 3922
(2010/05/01)
-
- Aqueous sodium hydroxide promoted cross-coupling reactions of alkenyltrialkoxysilanes under ligand-free conditions
-
(Chemical Equation Presented) Fluoride-free cross-coupling reactions of alkenyltrialkoxysilanes with aryl iodides, bromides, and chlorides are performed on water using sodium hydroxide as activator at 120 °C under normal or microwave heating. This process occurs in the presence of Pd(OAc)2 or 4-hydroxyacetophenone oxime-derived palladacycle 1 as precatalysts under ligand-free conditions with low Pd loadings (0.01-1 mol %) and using tetra-n-butylammonium bromide as additive. Different commercially available vinylalkoxylsilanes can be cross-coupled under these reaction conditions to the corresponding styrenes, the best substrates being vinyltrimethoxy- or vinyltriethoxysilane. Alkenyltriethoxysilanes, prepared by Wilkinson-catalyzed hydrosilylation of alkynes with triethoxysilane, are stereospecifically arylated with aryl and vinyl halides under microwave irradiation in moderate to high β/α regioselectivity affording unsymmetrical stilbenes, alkenylbenzenes, and conjugate dienes, respectively. This simple procedure allows the palladium recycling from the aqueous phase during three runs by extractive separation of the products, which contain very low levels of Pd (21-27.5 ppm for an aryl iodide and up to 76 ppm for a bromide).
- Alacid, Emilio,Najera, Carmen
-
p. 2315 - 2322
(2008/09/19)
-
- Synthesis, reactivity, crystal structures and catalytic activity of new chelating bisimidazolium-carbene complexes of Rh
-
A series of new bridging, chelating and pincer N-heterocyclic carbenes of RhI and RhIII have been obtained under mild conditions. The compounds have been fully characterised and their crystal structures determined. The chelate-pincer
- Poyatos, Macarena,Mas-Marza, Elena,Mata, Jose A.,Sanau, Mercedes,Peris, Eduardo
-
p. 1215 - 1221
(2007/10/03)
-
- Ruthenium-catalyzed hydrosilylation of terminal alkynes: Stereodivergent synthesis of (E)- and (Z)-alkenylsilanes
-
Stereodivergent hydrosilylation of terminal alkynes (RC≡CH; R = Ph, p-tolyl, Cy, n-hexyl) with hydrosilanes (HSiMe2Ar; Ar=Ph, 3,5-(CF3)2C6H3, 4-CF3C6H4, 4-MeOC6H4) has been examined using ruthenium catalysts. (E)-selective reactions giving (E)-RCH=CHSiMe2Ar proceed in over 99% selectivity in the presence of a catalytic amount of RuHCl(CO)(PPh3)3. On the other hand, (Z)-selective reactions are successfully conducted in 91-99% selectivity by using Ru(SiMe2Ph)Cl(CO)(PPri3)2 as the catalyst. All reactions readily proceed at room temperature in high yields. (E)- and (Z)-styrylsilanes having a SiMe2 [C6H3-3,5-(CF3)2] group serve as good cross-coupling reagents with p-iodotoluene in the presence of tetrabutylammonium fluoride and [Pd(η3-allyl) Cl]2 catalyst.
- Katayama, Hiroyuki,Taniguchi, Ken,Kobayashi, Masayuki,Sagawa, Takashi,Minami, Tatsuya,Ozawa, Fumiyuki
-
p. 192 - 200
(2007/10/03)
-
- RhCl(PPh3)3/NaI catalyst system for hydrosilylation of 1-alkynes: Stereodivergent syntheses of E-and Z-alkenylsilanes with heteroatom substituents on silicon
-
Both (E)-and (Z)-alkenylsilanes are synthesized by the reaction of hydrosilanes and 1-alkynes catalyzed by RhCl(PPh3)3/NaI or RhI(PPh3)3 highly selectively.
- Mori, Atsunori,Takahisa, Eisuke,Kajiro, Hiroshi,Hirabayashi, Kazunori,Nishihara, Yasushi,Hiyama, Tamejiro
-
p. 443 - 444
(2007/10/03)
-
- SYNTHESIS OF DI-μ-CHLOROTETRAKIS(η2-METHYLENECYCLOPROPANE)DIRHODIUM AND ITS CATALYTIC ACTIVITY IN HYDROSILYLATION
-
Di-μ-chlorotetrakis(η2-methylenecyclopropane)dirhodium was synthesized.The new complex exhibited high catalytic activity in the hydrosilylation of alkenes and alkynes.
- Donskaya, N. A.,Yur'eva, N. M.,Voevodskaya, T. I.,Sigeev, A. S.,Beletskaya, I. P.
-
p. 853 - 859
(2007/10/02)
-
- RHODIUM(I)-MONO- UND -DIAZADIENEKOMPLEXE, SYNTHESE, SPEKTROSKOPISCHE CHARAKTERISIERUNG, OXIDATIVE ADDITIONSREAKTIONEN UND EINSATZ IN DER HOMOGENEN KATALYSE ZUR HYDROSILYLIERUNG
-
The reaction of(Rh(CO)2Cl)2 with di- and monoazadienes gives planar, four-coordinated rhodium(I) complexes Rh(CO)Cl(DAD) (III) and Rh(CO)Cl(MAD)2 (V), respectively, which catalyse the hydrosilylation of alkenes and alkynes.In a stereoselektive cis-addition symmetric internal alkynes give the corresponding silyl alkenes, while the catalytic addition of silane to terminal alkynes leads to the 2-silyl and cis-and trans-1-silyl-alkenes; their ratio depends on the controlling ligand and on the reaction conditions.With a stoichiometric amount of the silane the complexes III react under oxidative addition to give the rhodium(III) complexes Rh(H)(SiR3)(DAD)Cl (VI), which also catalyse the hydrosilylation.
- Brockmann, Monika,Dieck, Heindirk tom,Klaus, Juergen
-
p. 209 - 226
(2007/10/02)
-
- HOMOGENEOUS CATALYSIS. IX. HYDROSILYLATION USING TRIS(PENTANEDIONATO)RHODIUM(III)-TRIALKYLALUMINIUM AS CATALYST
-
The two component (Ziegler) catalyst -AlEt3 (or an analogue with an alternative cocatalyst) has been investigated for the hydrosilylation by SiHX3 of alkynes, dienes, alkenes, styrene, or allylbenzene at 60 deg C.Terminal alkynes did not yield adducts, but internal alkynes RCCR' gave products of cis-addition with SiHEt3 or SiHEt2Me (but not SiH(OEt)3), without regiospecificity for the case of R R'.Acyclic dienes gave 1/1 adducts with SiHX3 (X = Me, Et, OEt or OSiMe3; but not X = Ph), predominantly (or, for penta-1,3-diene, exclusively) the products of 1,4-addition.Among cyclic dienes, only cyclohexa-1,3- (or -1,4)-diene was hydrosilylated with SiHEt3 to yield cyclohex-2-enyltriethylsilane; cycloocta-1,3-diene was merely rearranged to the 1,5-isomer, norbornadiene was polymerised, and no reaction was observed with 2,5-dimethylhexa-2,4-diene.Internal straight-chain alkenes RR'C=CHR'', RR'C=CR''R''', or cyclohexene proved unreactive; however disubstituted olefins RCH=CHR' gave the terminal (isomerised) 1/1-adducts, e.g., n-C5H11SiEt3 from MeCH=CHEt and SiHEt3.Likewise terminal alkenes RCH=CH2 gave RCH2CH2SiX3 (X = Ph or OEt) or (X = Et) a mixture of isomeric 1/1 adducts.With styrene and SiHEt3, or to a lesser extent SiH(OR)3 (R = Me or Et), the dehydrogenative hydrosilylated material, the vinylsilane PhCH=CHSiX3, was the principial product with isomeric 1/1 adduct byproducts; with allylbenzene, likewise, PhCH2CH=CHSiX3 was a significant, but less important, component of the reaction mixture.Mechanistic pathways are proposed; for the dehydrogenative hydrosilylation of styrene, crucial steps are styrene insertion into a RhIII-SiX3 bond and a subsequent intramolecular hydrogen transfer, which are consistent with both a labelling experiment using SiDEt3 and the lack of dehydrogenation (under the reaction conditions) of PhCH2CH2SiEt3.
- Cornish, Andrew J.,Lappert, Michael F.
-
p. 153 - 168
(2007/10/02)
-