cas 18166-37-5, N-HEXYLTRIETHOXYSILANE | Articles data

Articles about 18166-37-5Total 35 be found

Article title
Article abstract
Author
Journal number and time
Download

CATALYSIS OF HYDROSILYLATION XI. RHODIUM(I)-SILOXYALKYLPHOSPHINE COMPLEXES; SYNTHESIS, CHARACTERISTICS AND CATALYTIC ACTIVITY
Rhodium(I) complexes with 1,5-cycloocatdiene (COD) and disiloxydiphosphines 2 where n = 1-3; (B-1, B-2, B-3, respectively)> and/or with trisiloxytriphosphine Ph2P(CH2)3(CH3)Si2 (C-2) were synthesized.Their composition and structure were determined using elemental analysis, molecular weight measurements and spectroscopic (IR, 1H NMR and vis) methods, and were then compared with the corresponding data for RuCl(COD)PPh3 (A) and RhCl(COD)2 (D).The analyitical and physico-chemical data all confirm the square planar geometry of the rhodium siloxyphosphine (the same as for rhodium triphenylphosphine) complexes with the general formula mZ where m =2 and Z =(CH3)2SiOSi(CH3)2 or m = 3 and Z = (CH3)2SiOSi(CH3)OSi(CH3)2. The structure is independent of the type of phosphine ligand, and the molar ratio of Rh : P is always 1 : 1. Catalytic activity of the complexes prepared was tested in the hydrosilylation of 1-hexene by triethoxysilane which showed a slight decrease in turnover number (A-C) compared with Wilkinson's catalyst (E) but the activation energies for the rhodium-siloxyphosphine complexes (B and C) are higher than those for the rhodium phosphine complexes (A and E).
Duczmal, Wojciech,Urbaniak, Wlodzimierz,Marciniec, Bogdan
p. 85 - 92
(1986)
Read Online

-
-
Magomedov,G.K.I. et al.
p. 29 - 36
(1978)
Read Online

Solvent-free hydrosilylation of alkenes and alkynes using recyclable platinum on carbon nanotubes
Platinum nanoparticles were stabilized at the surface of carbon nanotubes and the nanohybrid was valorized as a catalyst for the hydrosilylation of alkenes and alkynes. The heterogeneous catalyst operated under sustainable conditions (room temperature, no solvent, low catalyst loading, air atmosphere) and exhibited improved stabilty as recycling and reuse could be achieved for multiple consecutive reactions.
Jawale, Dhanaji V.,Geertsen, Valérie,Miserque, Frédéric,Berthault, Patrick,Gravel, Edmond,Doris, Eric
p. 815 - 820
(2021/02/09)

14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes
Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh(iii) devoid of agostic interactions. The complexes [X-Rh(κ3(P,Si,Si)PhP(o-C6H4CH2SiiPr2)2], where X = Cl (Rh-1), Br (Rh-2), I (Rh-3), OTf (Rh-4), Cl·GaCl3(Rh-5); derive from a bis(silyl)-o-tolylphosphine with isopropyl substituents on the Si atoms. All five complexes display a sawhorse geometry around Rh and exhibit similar spectroscopic and structural properties. The catalytic activity of these complexes and [Cl-Ir(κ3(P,Si,Si)PhP(o-C6H4CH2SiiPr2)2],Ir-1, in styrene and aliphatic alkene functionalizations with hydrosilanes is disclosed. We show thatRh-1catalyzes effectively the dehydrogenative silylation of styrene with Et3SiH in toluene while it leads to hydrosilylation products in acetonitrile.Rh-1is an excellent catalyst in the sequential isomerization/hydrosilylation of terminal and remote aliphatic alkenes with Et3SiH including hexene isomers, leading efficiently and selectively to the terminal anti-Markonikov hydrosilylation product in all cases. With aliphatic alkenes, no hydrogenation products are observed. Conversely, catalysis of the same hexene isomers byIr-1renders allyl silanes, the tandem isomerization/dehydrogenative silylation products. A mechanistic proposal is made to explain the catalysis with these M(iii) complexes.
Abeynayake, Niroshani S.,Donnadieu, Bruno,Gorla, Saidulu,Montiel-Palma, Virginia,Mu?oz-Hernández, Miguel A.,Zamora-Moreno, Julio
supporting information
p. 11783 - 11792
(2021/09/06)

Photo-initiation hydrosilylation reaction method
The invention discloses a photo-initiation hydrosilylation reaction method, and relates to a method for hydrosilylation. The method comprises the following steps: (1) using olefin and hydrogen-containing silane as reaction raw materials, or using vinyl polysiloxane and hydrogen-containing polysiloxane as reaction raw materials; and (2) performing a hydrosilylation reaction on the reaction raw materials under illumination conditions and under the action of a photo-initiation catalyst, wherein the photoinitiator is an aroylphosphine oxide compound, a co-initiator catalyst is also included in thephoto-initiation hydrosilylation reaction method, the co-initiator is cuprous halide, and the molar ratio of the haloaroylphosphine oxide compound to the cuprous halide is (1:0.01)-(1:1); and the light source for the illumination condition is ultraviolet light, and the molar ratio of olefinic bonds in the olefin or vinyl silicone oil to the aroylphosphine oxide compound is (400:1)-(100:1). Through the method, use of precious metal catalysts is avoided, the reaction conditions are mild, the system needs no heating, and reduction of energy consumption is facilitated; and the method has good universality of the reaction substrate, and the catalytic system has a wide source and easy storage.
-
Paragraph 0042-0043; 0048-0049; 0052-0055; 0072-0073

(2019/11/28)

Waste-free and efficient hydrosilylation of olefins
High purity silicone precursors can now be synthesized by hydrosilylation of solvent-free olefins catalyzed by a highly stable and active glass hybrid catalyst consisting of mesoporous organosilica microspheres doped with Pt nanoparticles. These findings open the door to the sustainable manufacture of silicone and a way to further reduce the amount of platinum in silicones, which are ubiquitous advanced polymers with multiple uses and applications.
Pandarus, Valerica,Ciriminna, Rosaria,Gingras, Geneviève,Béland, Fran?ois,Kaliaguine, Serge,Pagliaro, Mario
p. 129 - 140
(2019/01/11)

Preparation, characterization and evaluation of a series of heterogeneous platinum catalysts immobilized on magnetic silica with different acid ligands
Platinum was immobilized on magnetic silica gel by means of boronic, nitric, carboxylic or sulfuric acid ligands to give four heterogeneous Pt nano-catalysts, designated as Fe3O4@SiO2-BA@Pt, Fe3O4@SiO2-NA@Pt, Fe3O4@SiO2-CA@Pt and Fe3O4@SiO2-SA@Pt, respectively. Particles of these mono-dispersible Pt catalysts were 10–20?nm in size and could be separated for recycling by means of a magnet. Fe3O4@SiO2-BA@Pt (0.174?mmol/g Pt) showed the best catalytic activity and selectivity, which were better than Speier’s catalyst. Its turnover numbers were up to 1.7 × 106 and 1.1 × 106 for hydrosilylation of 1-hexene or styrene, respectively. This material could also catalyze the hydrosilylation of a broad range of alkenes and alkynes as substrates and methyldichlorosilane or triethoxysilane as silanes. Similar yields of 1-hexyl-methyldichlorosilane at the first and eighth runs (96.5% and 95.2%, respectively), together with a final Pt content of 0.171?mmol/g indicated the outstanding stability of Fe3O4@SiO2-BA@Pt under the catalytic reaction conditions.
Li, Laiming,Li, Youxin,Assefa, Aschenaki,Bao, James J.
p. 779 - 787
(2019/08/12)

Silicon-hydrogen addition reaction (by machine translation)
The invention relates to the field of organic chemistry, in order to solve the addition reaction catalyst with hydrogen in the presence of the problem, the invention provides a method for addition reaction, in order to olefin and three b oxygen radical hydrogen silicane as raw materials, in order to b [(1 - mPEG - 3 - alkyl 2 - diphenyl [...] halide) rhodium chloride] as the catalyst, heating 50 - 90 °C stirring for 4 - 6 hours, filtration, vacuum distillation fraction of, hydrogen addition product is obtained. This method of mild reaction conditions, security, high reaction conversion rate, β addition product selectivity is strong, it is convenient to separate the products and the catalyst, the catalyst can be recycled. (by machine translation)
-
Paragraph 0044; 0045

(2018/04/21)

Hydrosilylation reaction using recyclable platinum compound as catalyst
The present invention relates to the field of organic chemistry. In order to solve the problems existing in catalysts for a hydrosilylation reaction, the present invention provides a hydrosilylation reaction method. The method comprises the steps of using an olefin and triethoxysilane as raw materials and taking bis[(1-mPEG-3-alkyl-2-diphenylphosphinous imidazolium halide)platinum dichloride] as acatalyst, performing heating to 50-90 DEG C, performing a stirring reaction for 4-6 hours, performing filtration, performing vacuum distillation, and collecting fractions to obtain a hydrosilylationproduct. The reaction conditions of the method are mild and safe, the reaction conversion rate is high, the selectivity of a beta addition product is high, separation of the products and the catalystis convenient, and the catalyst can be recovered and reused.
-
Paragraph 0044; 0045

(2018/04/21)

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
p. 7 - 11
(2018/01/01)

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
(2018/02/27)

Discovering Partially Charged Single-Atom Pt for Enhanced Anti-Markovnikov Alkene Hydrosilylation
The hydrosilylation reaction is one of the largest-scale application of homogeneous catalysis and is widely used to enable the commercial manufacture of silicon products. However, considerable issues including disposable platinum consumption, undesired side reactions and unacceptable catalyst residues still remain. Here, we synthesize a heterogeneous partially charged single-atom platinum supported on anatase TiO2 (Pt1δ+/TiO2) catalyst via an electrostatic-induction ion exchange and two-dimensional confinement strategy, which can catalyze hydrosilylation reaction with almost complete conversion and produce exclusive adduct. Density functional theory calculations reveal that unexpected property of Pt1δ+/TiO2 originates from atomic dispersion of active species and unique partially positive charge Ptδ+ electronic structure that conventional nanocatalysts do not possess. The fabrication of single-atom Pt1δ+/TiO2 catalyst accomplishes a reasonable use of Pt through recycling and maximum atom-utilized efficiency, indicating the potential to achieve a green hydrosilylation industry.
Chen, Yuanjun,Ji, Shufang,Sun, Wenming,Chen, Wenxing,Dong, Juncai,Wen, Junfeng,Zhang, Jian,Li, Zhi,Zheng, Lirong,Chen, Chen,Peng, Qing,Wang, Dingsheng,Li, Yadong
supporting information
p. 7407 - 7410
(2018/06/11)

N-heterocyclic carbene platinum complexes functionalized with a polyether chain and silyl group: Synthesis and application as a catalyst for hydrosilylation
-
Zhang, Fengxiang,Bai, Ying,Yang, Xiaoling,Li, Jiayun,Peng, Jianjian
p. 1271 - 1278
(2017/10/18)

A silicon-based polyether chains containing N - heterocyclic carbene metal complex and its preparation method and application (by machine translation)
The invention relates to the field of organic chemistry, in order to solve the current used for olefin catalytic hydrogen addition reaction of the selectivity of the catalyst is not high and the problem of unstable the reaction process, the present invention provides a silicon-based polyether chainsN- Heterocyclic carbene metal complex and its preparation method, imidazole with the halogenated polyether chain compound reaction to obtain the polyether chain merit functionalized imidazole, then with the chloromethyl substituted silane reaction to obtain silicon-containing base imidazole ionic liquid, the ion liquid prepared under the action of the tertiary butyl alcohol potassium, in-situ reaction with the metal complexes to produce silicon-based polyether chainsN- Heterocyclic carbene metal complex. Complex as olefin addition reaction of the hydrogen in the catalyst, can be design and high selectivity, the reaction process is more stable, easy separation, can be circulation utilization is high. (by machine translation)
-
Paragraph 0041; 0042

(2017/06/13)

Si-O-Si chain-bridged N-heterocyclic carbine platinum complex, and preparation method and application thereof
The invention provides a [Si-O-Si] chain-bridged N-heterocyclic carbine platinum complex and a preparation method thereof to improve intermiscibility of a coordinated metal platinum catalyst with a reaction substrate in hydrosilation of olefin, belonging to the field of organic chemistry. The preparation method comprises the following steps: reacting imidazole with chloromethyl-terminated siloxane so as to obtain imidazole type ionic liquid and subjecting the obtained ionic liquid and a metal complex to an in-situ reaction under the action of potassium tert-butanolate so as to produce the [Si-O-Si] chain-bridged N-heterocyclic carbine platinum complex. The special composition and structure of the complex is favorable for improving the activity, selectivity and stability of a catalyst, and the catalyst can be easily separated from a product for recycling.
-
Paragraph 0040-0041

(2017/07/07)

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
p. 65 - 69
(2015/07/15)

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)

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
p. 59 - 63
(2014/06/09)

Study on the anti-sulfur-poisoning characteristics of platinum-acetylide- phosphine complexes as catalysts for hydrosilylation reactions
A series of platinum-acetylide-phosphine complexes were synthesized and their anti-sulfur-poisoning characteristics investigated. In comparison with Speier's and Karstedt's catalysts, the platinum-acetylide-phosphine complexes exhibited both higher catalytic activity and selectivity for the β-adduct for the hydrosilylation reactions under the same conditions. Furthermore, the complexes also exhibited a strong ability to resist to sulfur-poisoning. This indicated that the alkyne ligands containing the silyl group had a strong impact on the hydrosilylation reaction. Copyright
Li, Jiayun,Niu, Congbai,Peng, Jiajian,Deng, Yuan,Zhang, Guodong,Bai, Ying,Ma, Chao,Xiao, Wenjun,Lai, Guoqiao
p. 454 - 460
(2014/06/09)

Well-defined NHC-rhodium hydroxide complexes as alkene hydrosilylation and dehydrogenative silylation catalysts
Alkene hydrosilylation and dehydrogenative silylation reactions, mediated by [Rh(cod)(NHC)(OH)] complexes (cod = 1,5-cyclooctadiene; NHC = N-heterocyclic carbene) are described. The study details a comparison of the catalytic activity and steric characteristics of four rhodium complexes bearing different NHC ligands. The novel [Rh(cod)(Ii-PrMe)(OH)] complex (Ii-PrMe = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidine) was designed to improve the reactivity of Rh(i)-hydroxides and proved to be a successful promoter of hydrosilylation and dehydrogenative silylation, displaying good stereo- and regiocontrol. The Royal Society of Chemistry 2013.
Truscott, Byron J.,Slawin, Alexandra M. Z.,Nolan, Steven P.
p. 270 - 276
(2013/02/25)

Effect of carboxyl-functionalized imidazolium salts on the rhodium-catalyzed hydrosilylation of alkene
A series of carboxyl-functionalized imidazolium salts were synthesized. Hydrosilylation reaction of carboxyl-functionalized imidazolium salts (1b-4b, 1c-3c) exhibited higher levels of styrene conversion and higher levels of β-adduct selectivity. In particular, no ethylbenzene as hydrogenation product could be yielded at all when Rh(PPh3)3Cl/carboxyl- functionalized imidazolium inner salts (1c-3c), respectively, were used as the catalyst. The Rh(PPh3)3Cl/carboxyl-functionalized imidazolium salts catalyst system can be reused without noticeable loss of catalytic activity.
Ma, Chao,Li, Jiayun,Peng, Jiajian,Bai, Ying,Zhang, Guodong,Xiao, Wenjun,Lai, Guoqiao
p. 28 - 36
(2013/03/28)

Hydrosilylation reactions catalyzed by rhodium complexes with phosphine ligands functionalized with imidazolium salts
Hydrosilylation reactions of styrene with triethoxysilane catalyzed by rhodium complexes with phosphine ligands functionalized with imidazolium salts are reported. In comparison with Wilkinson's catalyst, Rh(PPh3) 3Cl, all of the present rhodium complexes with phosphines functionalized with imidazolium salts exhibit higher catalytic activity and selectivity.
Li, Jiayun,Peng, Jiajian,Wang, Diliang,Bai, Ying,Jiang, Jianxiong,Lai, Guoqiao
experimental part
p. 263 - 268
(2011/02/17)

Synthesis of rhodium N-heterocyclic carbene complexes and their catalytic activity in the hydrosilylation of alkenes in ionic liquid medium
Rhodium complexes bearing N-heterocyclic carbene (NHC) ligands were prepared from bis(η4-1,5-cyclooctadiene) dichlorodirhodium and 1-alkyl-3-methylimidazolium-2-carboxylate, and the catalytic properties of rhodium complexes prepared in the hydrosilylation of alkenes in ionic liquid media were investigated. It was found that both the catalytic activity and selectivity of the rhodium complexes bearing NHC ligands were influenced by the attached substituents of the imidazolium cation. Additionally, rhodium complexes bearing NHC ligands in ionic liquid BMimPF6 could be reused without noticeable loss of catalytic activity and selectivity.
Li, Jiayun,Peng, Jiajian,Bai, Ying,Lai, Guoqiao,Li, Xiaonian
experimental part
p. 2116 - 2121
(2011/06/22)

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)

Hydrosilylation catalyzed with Rh(PPh3)3Cl/ionic- liquid-functionalized SiO2
Ionic liquid-modified silica has been prepared by a one-pot reaction of activated silica, 3-chloropropyltriethoxysilane, and alkylimidazole or pyridine. It was found that the catalytic activity and β-adduct selectivity of the supported catalyst Rh(PPh3)3Cl/ionic-liquid-modified-SiO2 for the hydrosilylation reaction of alkenes with triethoxysilane was significantly improved. Furthermore, the catalyst system could be recovered easily.
Li, Jiayun,Peng, Jiajian,Bai, Ying,Hu, Yingqian,Qiu, Huayu,Lai, Guoqiao,Li, Xiaonian
experimental part
p. 484 - 490
(2010/07/05)

Phosphines with 2-imidazolium ligands enhance the catalytic activity and selectivity of rhodium complexes for hydrosilylation reactions
Phosphines with 2-imidazolium ligands can specifically vary their physical and chemical properties by altering the attached substituents. Rhodium complexes (1b-7b) exhibited excellent catalytic activity and selectivity for hydrosilylation of olefins. The selectivity of the β-adduct clearly increased when the length of the alkyl chain bound to the imidazolium cation increased. Rhodium complex 1b in BMimPF6 can be reused without noticeable loss of catalytic activity and selectivity.
Li, Jiayun,Peng, Jiajian,Bai, Ying,Zhang, Guodong,Lai, Guoqiao,Li, Xiaonian
experimental part
p. 431 - 436
(2010/05/03)

Hydrosilylation catalysed by a rhodium complex in a supercritical CO 2/ionic liquid system
The hydrosilylation of alkenes in a supercritical CO2 (scCO 2)/ionic liquid (IL) system was investigated. Rh(PPh 3)3Cl exhibited excellent catalytic activity and selectivity. KOtBu was used as an additive, and no hydrogenation by-product (alkane) was detected in the scCO2/IL system. During hydrosilylation in the scCO2/IL system, the reactants were possibly transferred into the IL phase by scCO2, in which the catalyst was dissolved. The products can be flushed with scCO2 after the reaction and the catalyst/IL system reused.
Li, Jiayun,Peng, Jiajian,Zhang, Guodong,Bai, Ying,Lai, Guoqiao,Li, Xiaonian
experimental part
p. 1330 - 1334
(2010/09/17)

Convenient synthesis of alkoxyhalosilanes from hydrosilanes
Selective dehydrogenative coupling of di- and trihydrosilanes with alcohols catalyzed by PdCl2 or NiCl2 afforded alkoxyhydro- and dialkoxyhydrosilanes in good yield. Further treatment of the resulting alkoxyhydrosilanes with carbon tetrachloride or allyl bromide in the presence of the same catalyst led to the formation of alkoxychloro- and alkoxybromosilanes, respectively. Similar reactions of dialkoxyhydrosilanes with carbon tetrachloride afforded dialkoxychlorosilanes in good yield, although contamination of small amounts of trialkoxysilanes and alkoxydichlorosilanes was detected in the products. Selective substitution of the alkoxyhalosilanes with nucleophiles is also reported.
Ohshita, Joji,Taketsugu, Ryosuke,Nakahara, Yuki,Kunai, Atsutaka
p. 3258 - 3264
(2007/10/03)

Catalytic activity of bis(dialkylamino)carbenium salts in hydrosilylation reactions
Bis(dialkylamino)carbenium salts {[(Me2N)2CCl]+}2MCl4 2- (M = Ni, Pd) and {[Me2NC(X)NR2]+}2PtCl62- (R = Me, All; X = H, Cl, Me) are efficient catalysts for hydrosilylation of allyl phenyl ether, triallylamine, allyl chloride, allylamine, and 1-octene with various hydrosilanes. The catalytic activity is dependent on the salt composition and the nature of the metal M, the saturated compound, and the hydrosilane used. The catalysts used are usually insoluble in the reaction mixture, active, and stable. In some cases, carbenium salts are more selective than Speier's catalyst. Novel catalysts, silica-immobilized dialkylaminocarbenium salts, have been prepared. The kinetics of the reaction have been considered.
Chernyshev,Belyakova,Sheludyakov,Shevchenko
p. 1003 - 1006
(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)

Catalytic Asymmetric Synthesis of Optically Active 2-Alkanols via Hydrosilylation of 1-Alkenes with a Chiral Monophosphine-Palladium Catalyst
-
Uozumi, Yasuhiro,Hayashi, Tamio
p. 9887 - 9888
(2007/10/02)

Ruthenium Complexes with Diazadienes VII. 1,5-Cyclooctadiene-1,4-diaza-1,3-diene Hydridoruthenium Complexes (COD)(DAD)Ru(H)Cl: Synthesis, Structure and Catalytic Properties
Displacement of piperidine from Ru(COD)(piperidine)-trans-(H)Cl (I) by 1,4-diaza-1,3-dienes (DAD: RN=CR'CR'=NR) gives the complexes cis-Ru(COD)(DAD)(H)Cl (III).With relatively bulky DAD ligands the complexes III are unstable and are converted into compounds IV, which are also formed from III on heating.Complexes III are not accessible from Ru(COD)(DAD)Cl2(V).If the analogous starting material involving a cycloheptatriene Ib in place of the COD ligand is used, a piperidide anion is preserved as a ligand instead of a hydride.In the room temperature 1H NMR spectra of rigid asymmetric III all twelve hydrogen atoms of the COD ligand can be seen separately.A full assignment has been made by use of 2D-H/H-correlated spectra.The highest field resonance (1.2 ppm) is assigned to an olefinic H atom, shielded by the DAD chelate.Complexes III catalyse the isomerization of terminal alkenes to a cis/trans mixture (20/80) of internal alkenes.During the catalytic hydrosilylation of 1-alkenes this isomerization is a competing side reaction.Thermal decomposition of III gives free 1,3-COD; the decomposition under hydrogen gives cyclooctane stoichiometrically.In catalytic experiments III is found to catlyse the isomerization of 1,5-COD to 1,3-COD via 1,4-COD.Under hydrogen pressure (20 bar), III catalyses the hydrogenation of 1-hexene and cyclohexene.Four different ways in which one, two,or three 'vacant site' can be generated starting from III are discussed.
Dieck, Heindirk tom,Kleinwaechter, Ingo,Haupt, Erhard T. K.
p. 237 - 248
(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)

CATALYSIS OF HYDROSILYLATION. VII. CATALYSIS OF HYDROSILYLATION OF C=C BONDS BY RUTHENIUM PHOSPHINE COMPLEXES
A full account of the catalysis of hydrosilylation of the C=C bond in olefins, their derivatives with functional groups as well as in vinyl-trisubstituted silanes by ruthenium(II) and ruthenium(III) phosphine precursors is given.The ruthenium complexes are far more efficient catalysts for the hydrosilylation of 1-alkenes and vinyl-substituted silanes than for the substituted olefins and unsaturated esters.General features characterizing all hydrosilylation reactions catalyzed by the above catalysts are as follows: the reaction proceeds with alkoxy-substituted silanes(also with vinylsilanes) in the absence of solvent, and is enhanced (for RuII and olefins occurs exclusively) in the presence of molecular oxygen.Two general mechanisms are proposed for hydrosilylation of olefins and of vinylsilanes, respectively, which account for most of the experimental observations.
Marciniec, Bogdan,Gulinski, Jacek
p. 349 - 362
(2007/10/02)

IR-SPECTRAL INVESTIGATION OF THE HYDROSILYLATION OF OLEFINS IN PRESENCE OF METAL CARBONYLS
-
Magomedov, G. K.-I.,Druzhkoba, G. V.,Shkol'nik, O. V.,Nikitin, V. S.,Shestkova, T. A.,Bizyukova, N. M.
p. 1641 - 1645
(2007/10/02)

AN ACTIVE AND STABLE HYDROSILYLATION CATALYST: A SILICA SUPPORTED POLY-γ-MERCAPTOPROPYLSILOXANE-PLATINUM COMPLEX
A silica-supported poly-γ-mercaptopropylsiloxane-platinum complex was prepared and used as hydrosilylation catalyst with 1-hexene and acetylene.When it was used as the catalyst for addition of triethoxysilane to 1-hexene at 80 deg C or room temperature, the product was n-hexyltriethoxysilane only, and the catalyst could be reused over twenty times (turnover numbers achieved were about 10.000) without any appreciable loss in the catalytic activity.The addition of triethoxysilane to acetylene by this catalyst at 80 deg C or room temperature under an atmospheric pressure gave vinyltriethoxysilane and bis(triethoxysilyl)ethane in good yields.
Wang, Lin-Zhi,Jiang, Ying-Yan
p. 39 - 44
(2007/10/02)