- THE PROCESS FOR THE PREPARATION AND USE OF HAIR TREATMENT COMPOSITIONS CONTAINING ORGANIC C1-C6 ALKOXY SILANES
-
The subject of the present application is a method for the preparation and use of an agent for the treatment of keratinous material, in particular human hair, comprising the following steps: (1) Mixing one or more organic C1-C6 alkoxy silanes with water,(2) optionally, partial, or complete removal from the reaction mixture of the C1-C6 alcohols liberated by the reaction in step (1),(3) if necessary, addition of one or more cosmetic ingredients,(4) Filling of the preparation into a packaging unit,(5) Storage of the preparation in the packaging unit for a period of at least about 5 days; and(6) Application of the preparation on the keratinous material.
- -
-
-
- Cobalt bis(2-ethylhexanoate) and terpyridine derivatives as catalysts for the hydrosilylation of olefins
-
A simple method for the hydrosilylation of olefins by using air-stable cobalt catalysts is developed. The catalyst system is composed of simple, cheap, and readily available cobalt(II) salts and well-defined terpyridine derivatives as cocatalysts or ligands, and the hydrosilylation processes can be processed smoothly under mild conditions without either Grignard reagents or NaHBEt3 as activator.
- Dai, Zinan,Yu, Zehao,Bai, Ying,Li, Jiayun,Peng, Jiajian
-
-
- Efficient magnetically separable heterogeneous platinum catalyst bearing imidazolyl schiff base ligands for hydrosilylation
-
Reported herein is a magnetically separable heterogeneous nano catalyst Fe3O4@SiO2-biIMI- PtCl2, which is prepared by firstly applying a SiO2 coating onto readily synthesized magnetite nanoparticles via the hydrolysis condensation of tetraethyl orthosilicate (TEOS) under basic conditions, then modifying it using aminopropyl triethoxysilane and bis(imidazole) aldehyde, and finally incorporating a PtCl2 complex via coordination chemistry. The chemical structure and morphology of the nanocatalyst as well as the valence state and content of platinum within this catalyst were carefully characterized. This catalyst can mediate the hydrosilylation between 1-octene and hydrosilane, with the conversion of 1-octene reaching up to 99%, and it shows good regioselectivity as only β-adducts are identified. In addition, this catalyst can be reused for at least 5 cycles. The hydrosilylation reaction between different olefins and hydrosilanes can also be efficiently mediated by Fe3O4@SiO2-biIMI-PtCl2.
- Huo, Yingpeng,Hu, Jiwen,Tu, Yuanyuan,Huang, Zhenzhu,Lin, Shudong,Luo, Xiaojiong,Feng, Chao
-
-
- Platinum-Pyridine Schiff base complexes immobilized onto silica gel as efficient and low cost catalyst for hydrosilylation
-
A heterogeneous platinum catalyst with tridentate pyridine Schiff base ligands supported on silica gel is reported. The catalyst was fully characterized via FTIR, solid-state 13C NMR spectroscopy, X-ray photoelectron spectroscopy (XPS), N2 adsorption/desorption analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The catalyst showed potential application in mediating hydrosilylation reactions between olefins and hydrosilanes, and it can be reused for at least five cycles.
- Huo, Yingpeng,Hu, Jiwen,Liu, Feng,Wu, Jiapei,Zhang, Yikun,Zhang, Yalan,Wang, Qianyi
-
p. 812 - 818
(2021/07/25)
-
- Method of manufacturing organic silicon compound (by machine translation)
-
[Problem] to efficiently producing method of an organic silicon compound. The hydrosilane compounds in the presence of the catalyst in a reaction step [a] an alkene containing an organic silicon compound which, in the reaction process, the catalyst used is iron complex compound represented by the formula. R1 And R2 C each independently1 - C6 The hydrocarbon group, which may have a substituent C1 - C12 The aromatic hydrocarbon group, or a halogen atom, R3 C each independently1 - C12 Alkyl group, or a substituent which may be C6 - C12 The aromatic hydrocarbon group, X is independently a halogen atom, C1 - C12 Alkoxy, - OC (O) R6 (R6 C is1 - C12 The hydrocarbon group), or a trialkylsilyl group which may have a C1 - C12 Hydrocarbon group, is an integer of 0 - 4 n1, is an integer of 0 - 5 n2. [Drawing] no (by machine translation)
- -
-
Paragraph 0059-0063
(2020/05/07)
-
- Platinum-Imidazolyl Schiff Base Complexes Immobilized in Periodic Mesoporous Organosilica Frameworks as Catalysts for Hydrosilylation
-
An imidazolyl Schiff base-containing periodic mesoporous organosilica (PMO) was synthesized via co-condensation reactions between a newly prepared bis (imidazolyl)imine-bridged bis silane and tetraethyl orthosilicate in the presence of cetyltrimethyl ammonium bromide as a soft template. The resultant as-synthesized PMO was then employed as a solid support for platinum catalysts. This complex was fully characterized via various techniques including FTIR, solid-state13C NMR, and 29Si-NMR spectroscopy, as well as N2 adsorption/desorption analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) methods. In addition, the catalyst was proven to efficiently mediate hydrosilylation reactions between olefins and hydrosilanes, and it can be reused for at least five cycles without significant loss of activity.
- Huo, Yingpeng,Hu, Jiwen,Tu, Yuanyuan,Huang, Zhenzhu,Lin, Shudong,Hu, Yangfei,Feng, Chao
-
-
- Titanium-catalyzed hydrosilylation of olefins: A comparison study on Cp2TiCl2/Sm and Cp2TiCl2/LiAlH4 catalyst system
-
Hydrosilylation of olefins catalyzed by Cp2TiCl2/Sm (Cp = cyclopentadienyl) under solvent free conditions have been investigated. By using Cp2TiCl2/Sm as catalyst system, β-adducts and hydrogenation products were detected. Hydrosilylation of olefins catalyzed by Cp2TiCl2/LiAlH4 under room temperature has also been studied. The influence of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) on Cp2TiCl2/Sm and Cp2TiCl2/LiAlH4, respectively, indicated that hydrosilylation of olefins catalyzed with Cp2TiCl2/Sm went through a free radical reaction pathway while a coordination mechanism was applied for Cp2TiCl2/LiAlH4 catalyst system.
- Yang, Xiaoling,Bai, Ying,Li, Jiayun,Liu, Yu,Peng, Jiajian,Li, Tianbo,Lang, Rui,Qiao, Botao
-
-
- The catalytic activity of alkali metal alkoxides and titanium alkoxides in the hydrosilylation of unfunctionalized olefins
-
The catalytic activities of titanium alkoxides and alkali metal alkoxides for hydrosilylation of unfunctionalized olefins have been studied. Titanium(IV) alkoxides showed excellent catalytic activity, while alkali metal alkoxides have low catalytic activity for the hydrosilylation of olefins. However, by using titanocene dichloride as an additive, alkali metal alkoxides showed also excellent catalytic property for hydrosilylation. In comparison with titanium alkoxides, no α-adduct was obtained by using alkali metal alkoxides/Cp2TiCl2 as catalysts.
- Yang, Xiaoling,Bai, Ying,Li, Jiayun,Liu, Yu,Peng, Jiajian,Li, Tianbo,Lang, Rui,Qiao, Botao
-
-
- Regiodivergent hydrosilylation, hydrogenation, [2π + 2π]-cycloaddition and C-H borylation using counterion activated earth-abundant metal catalysis
-
The widespread adoption of earth-abundant metal catalysis lags behind that of the second- and third-row transition metals due to the often challenging practical requirements needed to generate the active low oxidation-state catalysts. Here we report the development of a single endogenous activation protocol across five reaction classes using both iron- and cobalt pre-catalysts. This simple catalytic manifold uses commercially available, bench-stable iron- or cobalt tetrafluoroborate salts to perform regiodivergent alkene and alkyne hydrosilylation, 1,3-diene hydrosilylation, hydrogenation, [2π + 2π]-cycloaddition and C-H borylation. The activation protocol proceeds by fluoride dissociation from the counterion, in situ formation of a hydridic activator and generation of a low oxidation-state catalyst.
- Agahi, Riaz,Challinor, Amy J.,Dunne, Joanne,Docherty, Jamie H.,Carter, Neil B.,Thomas, Stephen P.
-
p. 5079 - 5084
(2019/05/24)
-
- 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)
-
- 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 0048; 0049
(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 0048; 0049
(2018/04/21)
-
- Highly-active, graphene-supported platinum catalyst for the solventless hydrosilylation of olefins
-
Herein we report the development of the first graphene-supported platinum catalyst that has demonstrated exceptional catalytic activity and stability for hydrosilylation reactions of olefins (TOF 4.8 × 106 h-1, TON = 9.4 × 106). The catalyst also exhibited functional group tolerance over a broad range of industrially relevant substrates with minimal metal leaching. In addition, the catalyst system was successfully translated into a packed bed platform for continuous hydrosilylation reactions.
- Kong, Caleb J.,Gilliland, Stanley E.,Clark, Brian R.,Gupton, B. Frank
-
supporting information
p. 13343 - 13346
(2018/12/13)
-
- Cobalt Catalysts for Alkene Hydrosilylation under Aerobic Conditions without Dry Solvents or Additives
-
Alkene hydrosilylation is typically performed with Pt catalysts, but inexpensive base-metal catalysts would be preferred. Here, we report a simple method for the use of air-stable cobalt catalysts for anti-Markovnikov alkene hydrosilylation that can be used under aerobic conditions without dry solvents or additives. These catalysts can be generated from low-cost commercially available materials. In addition, these catalysts possess good catalytic ability for both hydrosilanes and hydroalkoxysilanes. Finally, a mechanistic study demonstrates that the silane and the catalyst generate a Co–H species in the course of the reaction, which has been observed by in situ Raman spectroscopy.
- Gutiérrez-Tarri?o, Silvia,Concepción, Patricia,O?a-Burgos, Pascual
-
supporting information
p. 4867 - 4874
(2018/11/25)
-
- Manganese-Catalyzed Hydrofunctionalization of Alkenes
-
The manganese-catalyzed hydrosilylation and hydroboration of alkenes has been developed using a single manganese(II) precatalyst and reaction protocol. Both reactions proceed with excellent control of regioselectivity and in high yields across a variety of sterically and electronically differentiated substrates (25 examples). Alkoxide activation, using NaOtBu, was key to precatalyst activation and reactivity. Catalysis was achieved across various functional groups and on gram-scale for both the developed methodologies with catalysts loadings as low as 0.5 mol %.
- Carney, Jonathan R.,Dillon, Barry R.,Campbell, Leonie,Thomas, Stephen P.
-
supporting information
p. 10620 - 10624
(2018/07/31)
-
- Fe and Co Complexes of Rigidly Planar Phosphino-Quinoline-Pyridine Ligands for Catalytic Hydrosilylation and Dehydrogenative Silylation
-
Co and Fe dihalide complexes of a new rigidly planar PNN ligand platform are prepared and examined as precatalysts for hydrosilylation of alkenes. Lithiation of Thummel's 8-bromo-2-(pyrid-2′-yl)quinoline followed by treatment with (i-Pr)2PCl and (C6F5)2PCl afforded the phosphine-quinoline-pyridine ligands, abbreviated RPQpy for R = i-Pr and C6F5, respectively. These ligands form 1:1 adducts with the dichlorides and dibromides of iron and cobalt. Crystallographic characterization of FeBr2(iPrPQpy), FeBr2(ArFPQpy), CoCl2(iPrPQpy), CoBr2(iPrPQpy), and CoCl2(ArFPQpy) confirmed that the M-P-C-C-N-C-C-N portion of these complexes is planar within 0.078 ? unlike previous generations of PNN complexes where deviations from planarity were ~0.35 ?. Bond distances as well as magnetism indicate that the Fe complexes are high spin and the cobalt complexes are high spin or participate in spin equilibria. Also investigated were the NNN analogues of the RPQpy ligands, wherein the phosphine group was replaced by the mesityl ketimine. The complexes FeBr2(MesNQpy) and CoCl2(MesNQpy) were characterized crystallographically. Reduction of MX2(RPQpy) complexes with NaBHEt3 generates catalysts active for anti-Markovnikov silylation of simple and complex 1-alkenes with a variety of hydrosilanes. Catalysts derived from MesNQpy exhibited low activity. Fe-RPQpy derived catalysts favor hydrosilylation, whereas Co-RPQpy based catalysts favor dehydrogenative silylation. Catalysts derived from CoX2(iPrPQpy) convert hydrosilanes and ethylene to vinylsilanes. Related experiments were conducted on propylene to give propenylsilanes.
- Basu, Debashis,Gilbert-Wilson, Ryan,Gray, Danielle L.,Rauchfuss, Thomas B.,Dash, Aswini K.
-
p. 2760 - 2768
(2018/09/10)
-
- 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
-
-
- Tuning the redox non-innocence of a phenalenyl ligand toward efficient nickel-assisted catalytic hydrosilylation
-
In this report, a ligand-redox assisted catalytic hydrosilylation has been investigated. A phenalenyl ligand coordinated nickel complex has been utilized as an electron reservoir to develop a base metal-assisted catalyst, which very efficiently hydrosilylates a wide variety of olefin substrates under ambient conditions. A mechanistic investigation revealed that a two-electron reduced phenalenyl based biradical nickel complex plays the key role in such catalysis. The electronic structure of the catalytically active biradical species has been interrogated using EPR spectroscopy, magnetic susceptibility measurements, and electronic structure calculations using a DFT method. Inhibition of the reaction by a radical quencher, as well as the mass spectrometric detection of two intermediates along the catalytic loop, suggest that a single electron transfer from the ligand backbone initiates the catalysis. The strategy of utilising the redox reservoir property of the ligand ensures that the nickel is not promoted to an unfavorable oxidation state, and the fine tuning between the ligand and metal redox orbitals elicits smooth catalysis.
- Vijaykumar, Gonela,Pariyar, Anand,Ahmed, Jasimuddin,Shaw, Bikash Kumar,Adhikari, Debashis,Mandal, Swadhin K.
-
p. 2817 - 2825
(2018/03/21)
-
- 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
-
-
- 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)
-
- Mode of activation of cobalt(II) amides for catalytic hydrosilylation of alkenes with tertiary silanes
-
Cobalt(II) complexes capable of catalyzing alkene hydrosilylation in the absence of external activators are rarely known, and their activation mode has remained poorly understood. We present here that cobalt(II) amide complexes, [Co(N(SiMe3)2)2] and its NHC adducts [(NHC)Co(N(SiMe3)2)2] (NHC = N-heterocyclic carbene), are effective catalysts for the hydrosilylation of alkenes with tertiary silanes. Mechanistic studies revealed that cobalt(II) amides can react with hydrosilane to form cobalt(I) species, silylamide, and hydrogen, which serves as the entry to the genuine catalytically active species, presumably cobalt(I) species, for the cobalt-catalyzed hydrosilylation reaction.
- Liu, Yang,Deng, Liang
-
supporting information
p. 1798 - 1801
(2017/02/15)
-
- Activation and discovery of earth-abundant metal catalysts using sodium tert-butoxide
-
First-row, earth-abundant metals offer an inexpensive and sustainable alternative to precious-metal catalysts. As such, iron and cobalt catalysts have garnered interest as replacements for alkene and alkyne hydrofunctionalization reactions. However, these have required the use of air- and moisture-sensitive catalysts and reagents, limiting both adoption by the non-expert as well as applicability, particularly in industrial settings. Here, we report a simple method for the use of earth-abundant metal catalysts by general activation with sodium tert-butoxide. Using only robust air- and moisture-stable reagents and pre-catalysts, both known and, significantly, novel catalytic activities have been successfully achieved, covering hydrosilylation, hydroboration, hydrovinylation, hydrogenation and [2π+2π] alkene cycloaddition. This activation method allows for the easy use of earth-abundant metals, including iron, cobalt, nickel and manganese, and represents a generic platform for the discovery and application of non-precious metal catalysis.
- Docherty, Jamie H.,Peng, Jingying,Dominey, Andrew P.,Thomas, Stephen P.
-
p. 595 - 600
(2017/05/31)
-
- Rhodium(III) Catalyzed Solvent-Free Tandem Isomerization–Hydrosilylation From Internal Alkenes to Linear Silanes
-
The selective synthesis of linear silanes from internal alkenes or alkene mixtures is reported. Unsaturated 16 electrons hydrido–silyl–RhIII complexes are efficient catalysts for a tandem catalytic alkene isomerization–hydrosilylation reaction at room temperature under solvent-free conditions. Such a process would be of value to the chemical industry, as mixtures of internal aliphatic olefins are substantially cheaper and more readily available than the pure terminal isomers.
- Azpeitia, Susan,Garralda, María A.,Huertos, Miguel A.
-
p. 1901 - 1905
(2017/06/13)
-
- DEHYDROGENATIVE SILYLATION, HYDROSILYLATION AND CROSSLINKING USING PYRIDINEDIIMINE COBALT CARBOXYLATE CATALYSTS
-
A process for producing a silylated product comprises reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, to produce a dehydrogenative silylated product, a hydrosilylated product, or a combination of a dehydrogenative silylated product and a hydrosilylated product, wherein the catalyst is chosen from a pyridine diimine cobalt dicarboxylate complex or a cobalt carboxylate compound, and the process is conducted without pre-activating the catalyst via a reducing agent and/or without an initiator or promoter compound. The present catalysts have been found to be active in the presence of the silyl hydride employed in the silylation reaction.
- -
-
Page/Page column 40
(2017/02/24)
-
- HYDROSILYLATION REACTION CATALYST
-
A hydrosilylation reaction catalyst prepared from: a catalyst precursor comprising a transition metal compound, excluding platinum, belonging to group 8-10 of the periodic table, e.g., iron acetate, cobalt acetate, nickel acetate, etc.; and a ligand comprising an isocyanide compound such as t-butyl isocyanide. The hydrosilylation reaction catalyst has excellent handling and storage properties. As a result of using this catalyst, a hydrosilylation reaction can be promoted under gentle conditions.
- -
-
Paragraph 0224-0225; 0249-0252
(2017/12/27)
-
- 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 0038; 0039
(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 0051-0052; 0056
(2017/07/07)
-
- Bis(acetylacetonato)Ni(II)/NaBHEt3-catalyzed hydrosilylation of 1,3-dienes, alkenes and alkynes
-
The utility of commercially available Ni(II) salts, Ni(acac)2 (acac = acetylacetonato) (1a) and its derivatives bis(hexafluoroacetylacetonato)nickel(II) (1b) and bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel(II) (1c) as versatile hydrosilylation catalyst precursors is described. Complexes 1a-c catalyze 1,4-selective hydrosilylation of 1,3-dienes in the presence of NaBHEt3 at ambient temperature. The reactions exhibit good regioselectivity to give the branched isomers as major products. The catalytic system also catalyzes hydrosilylation of alkenes including industriary important siloxy-, amino-, and epoxy-substituted ones as well as both terminal and internal alkynes.
- Srinivas, Venu,Nakajima, Yumiko,Ando, Wataru,Sato, Kazuhiko,Shimada, Shigeru
-
-
- Base-Metal-Catalyzed Regiodivergent Alkene Hydrosilylations
-
A complementary set of base metal catalysts has been developed for regiodivergent alkene hydrosilylations: iron complexes of phosphine-iminopyridine are selective for anti-Markovnikov hydrosilylations (linear/branched up to >99:1), while the cobalt complexes bearing the same type of ligands provide an unprecedented high level of Markovnikov selectivity (branched/linear up to >99:1). Both systems exhibit high efficiency and wide functional group tolerance. Regiodivergent alkene hydrosilylation has been accomplished with high efficiency using a newly developed set of complementary base metal catalyst systems. An inversion of regioselectivity (linear/branched) from >99:1 to 1:99 is obtained when the iron version of the catalyst is exchanged for a cobalt-containing analogue.
- Du, Xiaoyong,Zhang, Yanlu,Peng, Dongjie,Huang, Zheng
-
supporting information
p. 6671 - 6675
(2016/06/08)
-
- Bench-Stable, Substrate-Activated Cobalt Carboxylate Pre-Catalysts for Alkene Hydrosilylation with Tertiary Silanes
-
High-spin pyridine diimine cobalt(II) bis(carboxylate) complexes have been synthesized and exhibit high activity for the hydrosilylation of a range of commercially relevant alkenes and tertiary silanes. Previously observed dehydrogenative silylation is suppressed with the use of sterically unencumbered ligands, affording exclusive hydrosilylation with up to 4000 TON. The cobalt precatalysts were readily prepared and handled on the benchtop and underwent substrate activation, obviating the need for external reductants. The cobalt catalysts are tolerant of epoxide, amino, carbonyl, and alkyl halide functional groups, broadening the scope of alkene hydrosilylation with earth-abundant metal catalysts.
- Schuster, Christopher H.,Diao, Tianning,Pappas, Iraklis,Chirik, Paul J.
-
p. 2632 - 2636
(2016/04/26)
-
- Alkene Hydrosilylation Using Tertiary Silanes with α-Diimine Nickel Catalysts. Redox-Active Ligands Promote a Distinct Mechanistic Pathway from Platinum Catalysts
-
Combination of the readily available α-diimine ligand, ((ArN=C(Me))2 Ar = 2,6-iPr2-C6H3), (iPrDI) with air-stable nickel(II) bis(carboxylates) generated a highly active catalyst exhibiting anti-Markovnikov selectivity for the hydrosilylation of alkenes with a variety of industrially relevant tertiary alkoxy- and siloxy-substituted silanes. A combination of the method of continuous variations with stoichiometric studies identified the formally Ni(I) hydride dimer, [(iPrDI)NiH]2 as the nickel compound formed following reduction of the carboxylate ligands. For the hydrosilylation of 1-octene with (EtO)3SiH, a rate law of [Ni]1/2[1-octene][(EtO)3SiH] in combination with deuterium-labeling studies establish dissociation of the nickel hydride dimer followed by fast and reversible alkene insertion into (iPrDI)NiH, consistent with turnover-limiting C-Si bond formation. The hydrosilylation of 1-octene with triethoxysilane, a reaction performed commercially in the silicones industry on a scale of >5000000 kg/year, was conducted on a 10 g scale with 96% yield and >98% selectivity for the desired product. Silicone cross-linking, another major industrial application of homogeneous hydrosilylation, was also demonstrated using the air-stable nickel and ligand precursors.
- Pappas, Iraklis,Treacy, Sean,Chirik, Paul J.
-
p. 4105 - 4109
(2016/07/12)
-
- Synthesis of a fumed silica-supported poly-3-(2-aminoethylamino)propylsiloxane platinum complex and its catalytic behavior in the hydrosilylation of olefins with triethoxysilane
-
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.
- Li, Ji,Zhang, Lei,Li, Tingting,Yang, Chunhui
-
p. 728 - 733
(2016/05/09)
-
- Metal-Organic Frameworks Stabilize Mono(phosphine)-Metal Complexes for Broad-Scope Catalytic Reactions
-
Mono(phosphine)-M (M-PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal-organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C-H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M-PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.
- Sawano, Takahiro,Lin, Zekai,Boures, Dean,An, Bing,Wang, Cheng,Lin, Wenbin
-
supporting information
p. 9783 - 9786
(2016/08/19)
-
- METHOD FOR PRODUCING ORGANOSILICON COMPOUND AND CATALYST COMPOSITION
-
PROBLEM TO BE SOLVED: To provide a method for producing an organosilicon compound by the hydrosilylation reaction of alkenes or alkynes using a new catalyst. SOLUTION: There is provided a method for producing an organosilicon compound in which a nickel complex compound represented by the following formula and a borane compound such as tri(pentafluorophenyl)borane or a hydride reducing agent such as sodium triethylhydroborate are blended in a reaction solution in the hydrosilylation reaction of alkenes such as 1-octene and butadiene or alkynes. (R1 each independently represents H or a hydrocarbon group having 1 to 15 carbon atoms substituted/unsubstituted with at least one atom selected from N, O, S or a halogen atom.) COPYRIGHT: (C)2016,JPOandINPIT
- -
-
Paragraph 0033; 0034
(2016/12/01)
-
- COBALT CATALYSTS AND THEIR USE FOR HYDROSILYLATION AND DEHYDROGENATIVE SILYLATION
-
Disclosed herein are cobalt complexes containing terpyridine ligands and chelating alkene-modified silyl ligands, and their use as hydrosilylation and/or dehydrogenative silylation and crosslinking catalysts. The cobalt complexes also exhibit adequate air stability for handling and manipulation.
- -
-
Page/Page column 21; 22
(2015/06/08)
-
- 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
-
-
- Chemoselective Alkene Hydrosilylation Catalyzed by Nickel Pincer Complexes
-
Chemoselective hydrosilylation of functionalized alkenes is difficult to achieve using base-metal catalysts. Reported herein is that well-defined bis(amino)amide nickel pincer complexes are efficient catalysts for anti-Markovnikov hydrosilylation of terminal alkenes with turnover frequencies of up to 83 000 per hour and turnover numbers of up to 10 000. Alkenes containing amino, ester, amido, ketone, and formyl groups are selectively hydrosilylated. A slight modification of reaction conditions allows tandem isomerization/hydrosilylation reactions of internal alkenes using these nickel catalysts.
- Buslov, Ivan,Becouse, Jeanne,Mazza, Simona,Montandon-Clerc, Mickael,Hu, Xile
-
supporting information
p. 14523 - 14526
(2016/01/25)
-
- 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)
-
- COSMETIC TREATMENT METHOD COMPRISING THE APPLICATION OF A COATING BASED ON AN AEROGEL COMPOSITION OF LOW BULK DENSITY
-
The present invention relates to a cosmetic treatment method comprising the formation of a coating on keratin fibres characterized in that it comprises: 1) the preparation of an aerogel precursor composition comprising:—at least one organic solvent chosen from acetone, C1-C4 alcohols, C1-C6 alkanes, C1-C4 ethers, which may or may not be perfluorinated, and mixtures thereof and at least one precursor compound that contains:—at least one atom chosen from silicon, titanium, aluminium and zirconium,—at least one hydroxyl or alkoxy function directly attached to the atom chosen from silicon, titanium, aluminium and zirconium by an oxygen atom, and,—optionally an organic group directly attached to the atom chosen from silicon, titanium, aluminium and zirconium by a carbon atom, 2) the removal of the solvent or solvents resulting in the formation of an aerogel composition having a bulk density less than or equal to 0.35 g/cm3, 3) the application to the keratin fibres of the aerogel composition resulting from step 2) or of the aerogel precursor composition resulting from step 1). Advantageously, the molar ratio between the precursor compounds and the solvent is at most 1/20.
- -
-
Paragraph 0067
(2014/02/15)
-
- 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
-
-
- Phosphinite-iminopyridine iron catalysts for chemoselective alkene hydrosilylation
-
A series of new pincer iron complexes with electron-donating phosphinite-iminopyridine (PNN) ligands has been prepared and characterized. These iron compounds are efficient and selective catalysts for the anti-Markovnikov alkene hydrosilylation of primary, secondary, and tertiary silanes. More importantly, the system exhibits unprecedented functional group tolerance with reactive groups such as ketones, esters, and amides. Furthermore, the iron-catalyzed alkene hydrosilylation was successfully applied to the synthesis of a valuable insecticide, silafluofen. The electronic properties and structures of the iron complexes have been studied by spectroscopies and computational methods. Overall, the iron catalysts may provide a low-cost and environmentally benign alternative to currently employed precious metal systems for alkene hydrosilylation.
- Peng, Dongjie,Zhang, Yanlu,Du, Xiaoyong,Zhang, Lei,Leng, Xuebing,Walter, Marc D.,Huang, Zheng
-
supporting information
p. 19154 - 19166
(2014/01/17)
-
- 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
-
-
- Process of Manufacturing Organosilicon Products with Improved Quality Using Heterogeneous Precious Metal Catalysts
-
A process for manufacturing an organosilicon product having a stabilized low color and no formation of black particles during storage includes (a) reacting an unsaturated compound with a silicon compound having a reactive Si—H bond under hydrosilylation conditions in a reaction zone in the presence of a heterogeneous precious metal catalyst to provide an organosilicon product having a color of less than 40 pt/co; (b) separating the heterogeneous precious metal catalyst from the organosilicon product; and (c) recovering the heterogeneous precious metal catalyst.
- -
-
Paragraph 0315; 0316; 0317; 0318; 0319; 0320; 0321; 0322;
(2013/05/09)
-
- Non-precious Metal-based Hyrdosilylation Catalysts Exhibiting Improved Selectivity
-
Disclosed herein is the use of manganese, iron, cobalt, or nickel complexes containing tridentate pyridine di-imine ligands as hydrosilylation catalysts. These complexes are effective for efficiently catalyzing hydrosilylation reactions, as well as offering improved selectivity and yield over existing catalyst systems.
- -
-
Paragraph 0105
(2013/06/28)
-
- Iron catalysts for selective anti-Markovnikov alkene hydrosilylation using tertiary silanes
-
Alkene hydrosilylation, the addition of a silicon hydride (Si-H) across a carbon-carbon double bond, is one of the largest-scale industrial applications of homogeneous catalysis and is used in the commercial production of numerous consumer goods. For decades, precious metals, principally compounds of platinum and rhodium, have been used as catalysts for this reaction class. Despite their widespread application, limitations such as high and volatile catalyst costs and competing side reactions have persisted. Here, we report that well-characterized molecular iron coordination compounds promote the selective anti-Markovnikov addition of sterically hindered, tertiary silanes to alkenes under mild conditions. These Earth-abundant base-metal catalysts, coordinated by optimized bis(imino)pyridine ligands, show promise for industrial application.
- Tondreau, Aaron M.,Atienza, Crisita Carmen Hojilla,Weller, Keith J.,Nye, Susan A.,Lewis, Kenrick M.,Delis, Johannes G. P.,Chirik, Paul J.
-
scheme or table
p. 567 - 570
(2012/06/18)
-
- A novel fumed silica-supported nitrogenous platinum complex as a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane
-
A novel fumed silica-supported nitrogenous platinum complex was conveniently prepared from cheap γ-aminopropyltriethoxysilane via immobilization on fumed silica in toluene, followed by a reaction with hexachloroplatinic acid. The title complex was characterized by fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). It was found that the complex is an efficient and stable catalyst for the hydrosilylation of olefins with triethoxysilane. The title platinum complex could be separated by simple filtration and reused several times without any appreciable loss in the catalytic activity. Crown Copyright
- Li, Ji,Yang, Chunhui,Zhang, Lei,Ma, Tianlong
-
experimental part
p. 1845 - 1849
(2011/06/19)
-
- 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)
-