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41.
Marcin Jankowiak 《Journal of organometallic chemistry》2005,690(20):4478-4487
Catalytic reactivity of Si-H bond of di-, trisiloxanes with allyl chloride in the presence of platinum catalyst has been examined. Hydrosilylation process competes with hydrogen substitution by chlorine and/or propenyl group. The effect of the reaction conditions as well as structure of siloxane on the yield and selectivity of the number of products has been discussed. Several consecutive-competitive processes have been identified. The results obtained can be helpful in the study of the catalytic hydropolysiloxanes reactions with allyl derivatives-systems of great practical importance, to produce commercial functionalized silicones. 相似文献
42.
Wilkinson's complex [RhCl(PPh3)3], anchored to phosphino-organosiloxane macromolecules grafted onto chrysotile asbestos, appeared to be an unusually effective and selective catalyst for the synthesis of vinylsilanes via gas-phase hydrosilylation of acetylene, particularly by methyldichlorosilane in a continuous-flow microreactor as well as in a laboratory reactor. Catalytic and kinetic parameters show an advantage for the catalyst based on the chrysotile-polyorganosiloxane support (catalyst CHR–Rh) over the phosphinated silica (catalyst A). 相似文献
43.
Chelating biscarbene ligands increase the stability of metal-organic catalyst systems. The catalytic activities of seven structurally different platinum(II)-bis-NHC-complexes in the hydrosilylation of alkenes have been investigated and compared with the catalytic activity of the Karstedt catalyst and of a highly active platinum(0)-NHC-complex. It is shown that a fine-tuning of the catalytic activity of the platinum(II)-bis-NHC-complexes is possible. The synthesis of a platinum(II)-bis-NHC-complex with similar activity, but additional advantages compared to the Karstedt catalyst, is reported. The solid state structure of 1,1-[Bis(3,3′-(4-methoxyphenyl)-1,1′-1H-imidazolium-2,2′-ylidene)methanediyl]platinum(II)-dichloride is presented. 相似文献
44.
The concept of “Frustrated Lewis pairs” (FLPs), which emerged from the discovery that H2 can be reversibly activated by combinations of sterically encumbered Lewis acids and bases. Since then, the field of FLP chemistry has expanded enormously. One of the most remarkable achievements is the development of FLP catalysts for hydrogenation, which are environmentally friendly and have potential industrial application prospects. In recent years, this unique catalysis concept has pushed the study of FLP chemistry to a new direction: heterogeneous FLP catalysts. This review outlines the recent research progress of new strategies to design and synthesize heterogeneous FLPs for hydrogenation reaction, and prospects the development of novel heterogeneous FLP catalysts. 相似文献
45.
α-{ 3-[2-hydroxy-3-(N-methyl-N-hydroxyethylamino)propoxy]propyl }-α-butylpolydimethylsiloxanes III with various molecu- lar weights were prepared by epoxy addition of α-[3-(2,3-epoxy-propoxy)propyl]-α-butylpolydimethylsiloxanes Ⅱ and N- methylmonoethanolamine. At each step, the outcome compounds were characterized through FT-IR and NMR spectra, the results showed that each step was successfully carried out and objective products were achieved. 相似文献
46.
Prof. Takayuki Nakajima Mizuki Takubo Yurika Komura Yuki Maeda Miwa Sato Maki Zouda Prof. Tomoaki Tanase 《欧洲无机化学杂志》2023,26(9):e202200648
A new series of cationic heterodinuclear complexes, [M1M2Cl2(meso-dpmppp)(RNC)2]PF6 (M1=Ni, M2=Rh, R=tBu ( 1 a ); M1=Pd, M2=Rh, R=tBu ( 2 a ), Xyl ( 2 b ); M1=Pt, M2=Rh, R=tBu ( 3 a ), Xyl ( 3 b ); M1=Pd, M2=Ir, R=tBu ( 4 a )), supported by a tetradentate phosphine ligand, meso-Ph2PCH2P(Ph)(CH2)3P(Ph)CH2PPh2 (meso-dpmppp), were synthesized by stepwise reactions of meso-dpmppp with NiCl2 ⋅ 6H2O or MCl2(cod) (M=Pd, Pt), forming mononuclear metalloligands of [M1Cl2(meso-dpmppp)], and with [M2Cl(cod)]2 (M2=Rh, Ir) and RNC (R=tBu, Xyl) in the presence of [NH4][PF6]. The related neutral PdRh complex, [PdRhCl3(meso-dpmppp)(XylNC)] ( 5 ), was also prepared. The structures of 1 – 5 were determined by X-ray analyses to contain two square planar d8 metal centers with face-to-face arrangement, where meso-dpmppp supports M1 and M2 metal ions in cis/trans-P,P coordination mode, combining cis-{M1P2Cl2} and trans-{M2P2(CNR)2} units. Complexes 1 – 4 showed an intence characteristic absorption around 422–464 nm derived from RhI→RNC MLCT transition (HOMO→LUMO+1), which are influenced by changing M1 (NiII, PdII, PtII) metal ions since HOMO composed of dσ* orbitals appreciably destabilized by changing M1 from Ni to Pd, and Pt. The electronic structures of 1 a – 4 a were investigated on the basis of DFT calculations and NBO analyses to show weak but noticeable d8–d8 metallophilic interaction as empirical dispersion energy of 0.9–1.5 kcal/mol without M1–M2 covalent bonding interaction. In addition, 1 – 5 were utilized as catalysts for hydrosilylation of styrene, and the NiRh complex 1 a was found to show higher activity and chemo- and regioselectivity compared with 2 – 5 . 相似文献
47.
Ji Li Lei Zhang Tingting Li Chunhui Yang 《Phosphorus, sulfur, and silicon and the related elements》2016,191(5):728-733
A novel fumed silica-supported bidentate nitrogen platinum complex was conveniently prepared from N-(2-aminoethyl)-3-aminopropyltriethoxysilane via immobilization on fumed silica followed by a reaction with hexachloroplatinic acid. The title complex was systematically characterized and analyzed by Fourier Transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and specific surface area analysis (BET). The resulting title complex was found to be efficient and stable in catalyzing the hydrosilylation reaction of olefins with triethoxysilane. Furthermore, the polymeric platinum complex could be separated by simple filtration and reused four times without any appreciable loss of catalytic activity. 相似文献
48.
49.
A series of new silicon-containing poly(p-arylene vinylene)s(PAVs)with anthracene units in the main chain were synthesized by hydrosilylation reaction.The introduction of organosilicon units improved the solubility of the polymers,and theπ-πconjugation of polymeric chains was interrupted.These polymers behaved as blue-green light emitters with their fluorescence maximum at 447—499 nm and quantum yields in the range of 0.28-0.30 in solution. 相似文献
50.
Shu-wen Hu Zheng-cheng Zhang FanYi Shi-bi Fang Xin-feng Zhang Fu-mian Li Department of Chemistry Peking University Beijing China 《高分子科学》2000,(2):109-113
Solvent-free polymeric alkali-metal ion conductors, consisting of a comb-like polysiloxane with oligo(oxy-ethylene) side chains and pendant sulfate groups were synthesized by the hydrosilylation of allyl oligo(oxyethylene) sulfatesalt and allyl methoxy oligo(oxyethylene) with poly(methylhydrosiloxane). The factors influncing the ionic conductivity ofthe resulting polymer such as the electrolyte content and the nature of the alkali-metal were investigated. The temperaturedependence of conductivity was determined, and the ionic conductivity of the polymer follows the Vogel-Tammann-Fulcher(VTF) equation. 相似文献