- Silacyclopropylideneplatinum(0) Complex as a Robust and Efficient Hydrosilylation Catalyst
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The base-stabilized silacyclopropylidene 1 behaves as a versatile strongly nucleophilic ligand toward transition metals. The strong silylene-metal binding related to both increased σ-donating and π-accepting character of silylene 1 compared to N-heterocyc
- Troadec, Thibault,Prades, Amparo,Rodriguez, Ricardo,Mirgalet, Raphael,Baceiredo, Antoine,Saffon-Merceron, Nathalie,Branchadell, Vicen?,Kato, Tsuyoshi
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- The effect of the catalyst and the type of ionic liquid on the hydrosilylation process under batch and continuous reaction conditions
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Organofunctional silanes, siloxanes, and polysiloxanes are widely applied in industry. One of the most popular and commonly used processes for the synthesis of these compounds is based on the catalytic hydrosilylation reaction. However, even though this r
- Jankowska-Wajda,Kukawka,Smiglak,Maciejewski
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- Decoding catalytic activity of platinum carbene hydrosilylation catalysts
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A series of complexes of the formula [Pt(dvtms)(ImPy-R)] (dvtms = 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, ImPy-R = 2-R-imidazo[1,5-a]pyridine-3-ylidene; R = 4-cyanophenyl (4a), 4-trifluoromethylphenyl (4b), phenyl (4c), 4-methoxyphenyl (4d), mesityl (4
- Meister, Teresa K.,Kück, Jens W.,Riener, Korbinian,P?thig, Alexander,Herrmann, Wolfgang A.,Kühn, Fritz E.
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- A Dialkylsilylene-Pt(0) Complex with a DVTMS Ligand for the Catalytic Hydrosilylation of Functional Olefins
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A platinum(0) complex, bearing a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (DVTMS) and an isolable dialkylsilylene ligand, was successfully synthesized by the reaction between the dialkylsilylene and Karstedt’s catalyst. The downfield-shifted 29Si NMR resonance, the smaller 1JSi,Pt value, and the longer Si-Pt distance in this complex relative to the corresponding parameters in related bis(phosphine)-coordinated silylene-platinum complexes suggest weaker π-back-donation from the Pt center to the silylene, which is, however, still significant when compared to related DVTMS-ligated Pt complexes bearing N-heterocyclic carbenes, N-heterocyclic two-coordinate silylenes, or base-stabilized three-coordinate silylenes. The title complex displays excellent catalytic activity in the hydrosilylation of terminal olefins that contain functional groups such as epoxide and amine moieties.
- Iimura, Tomohiro,Akasaka, Naohiko,Iwamoto, Takeaki
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- Developing a Highly Active Catalytic System Based on Cobalt Nanoparticles for Terminal and Internal Alkene Hydrosilylation
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This work describes the development of easy-To-prepare cobalt nanoparticles (NPs) in solution as promising alternative catalysts for alkene hydrosilylation with the industrially relevant tertiary silane 1,1,1,3,5,5,5-heptamethyltrisiloxane (MDHM). The Co NPs demonstrated high activity when used at 30 °C for 3.5-7 h in toluene, with catalyst loadings 0.05-0.2 mol %, without additives. Under these mild conditions, a set of terminal alkenes were found to react with MDHM, yielding exclusively the anti-Markovnikov product in up to 99% yields. Additionally, we demonstrated the possibility of using UV irradiation to further activate these cobalt NPs not only to enhance their catalytic performances but also to promote tandem isomerization-hydrosilylation reactions using internal alkenes, among them unsaturated fatty ester (methyl oleate), to produce linear products in up to quantitative yields.
- Jakoobi, Martin,Dardun, Vincent,Veyre, Laurent,Meille, Valérie,Camp, Clément,Thieuleux, Chloé
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- Alkene Hydrosilylation Using Tertiary Silanes with α-Diimine Nickel Catalysts. Redox-Active Ligands Promote a Distinct Mechanistic Pathway from Platinum Catalysts
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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.
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- Iron catalysts for selective anti-Markovnikov alkene hydrosilylation using tertiary silanes
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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.
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- Second generation N-heterocyclic carbene-Pt(0) complexes as efficient catalysts for the hydrosilylation of alkenes
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A new class of benzimidazolylidene carbene-Pt(0) complexes was developed and used to efficiently catalyse the hydrosilylation of alkenes. The Royal Society of Chemistry 2005.
- Buisine, Olivier,Berthon-Gelloz, Guillaume,Briere, Jean-Francois,Sterin, Sebastien,Mignani, Gerard,Branlard, Paul,Tinant, Bernard,Declercq, Jean-Paul,Marko, Istvan E.
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- New approach to hydrosilylation reaction in ionic liquids as solvent in microreactor system
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Continuous flow-through reactors on a micro scale (microreactors) are being investigated as a new approach to chemical synthesis, due to significantly larger surface-to-volume ratios and micro-structured internal volumes, which allow for much more efficient heat exchange. Functionalized siloxanes, as one of the most important classes of organosilicon compounds, are widely applied in industry. Many of their synthetic methods are based on the catalytic process of hydrosilylation. In our studies, we investigated, as a model, the reaction between 1,1,1,3,5,5,5-heptamethyltrisiloxane and 1-octene, using the Karstedt catalyst dissolved in seven different ionic liquids. The reaction was carried out in batch and in the microreactor system. Studies have shown that the use of ionic liquids in general allows for catalyst recycling and reuse in subsequent reaction cycles. Moreover, the use of microreactors intensified the process, allowing a higher yield to be obtained than when using conventional batch reactions.
- Kukawka,Pawlowska-Zygarowicz,Dutkiewicz,Maciejewski,Smiglak
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- A general protocol for the synthesis of Pt-NHC (NHC = N-heterocyclic carbene) hydrosilylation catalysts
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A general, user-friendly synthetic route to [Pt(NHC)(L)Cl2] and [Pt(NHC)(dvtms)] (L = DMS, Py; DMS = dimethyl sulfide, dvtms = divinyltetramethylsiloxane, Py = pyridine) complexes has been developed. The procedure is applicable to a wide range of ligands and enables facile synthetic access to key Pt(0)- and Pt(ii)-NHC complexes used in hydrosilylation catalysis. This journal is
- Maliszewski, Benon P.,Tzouras, Nikolaos V.,Guillet, Sébastien G.,Saab, Marina,Beli?, Marek,Van Hecke, Kristof,Nahra, Fady,Nolan, Steven P.
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- Platinum-Catalyzed Alkene Hydrosilylation: Solvent-Free Process Development from Batch to a Membrane-Integrated Continuous Process
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The integration of a membrane separation protocol with the platinum-catalyzed hydrosilylation of olefins is investigated. The catalytic reaction is first optimized in batch where [Pt(IPr*)(dms)Cl2] (IPr=1,3-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]imidazol-2-ylidene, dms=dimethyl sulfide) demonstrates superior activity compared to the less sterically encumbered [Pt(SIPr)(dms)Cl2] (SIPr=1,3-bis(2,6-diisopropylphenyl)imidazolidine) congener. Filtration conditions are identified in membrane screening experiments. Hydrosilylation of 1-octene catalyzed by [Pt(IPr*)(dms)Cl2] is conducted in continuous mode and the platinum catalyst is separated efficiently over the commercially available Borsig oNF-2 membrane, all under solvent-free conditions. An advantage of this process is that both reaction and separation are coupled in a single step. Moreover, at the end of the process the intact catalyst was recovered in 80 % yield as an off-white solid without any further purification.
- Bayrakdar, Tahani A. C. A.,Maliszewski, Benon P.,Nahra, Fady,Ormerod, Dominic,Nolan, Steven P.
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- Highly efficient hydrosilylation catalysts based on chloroplatinate “ionic liquids”
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The reaction between ionic liquid [Cat]+Cl? (where Cat stands for 1-butyl-3-methylimidazolium, 1-butyl-2,3-dimethylimidazolium or 1-butyl-4-methylpyridinium)and the metal precursor ([PtCl2(cod)], PtCl4, K2[PtCl4]or K2[PtCl6])yielded two groups of derivatives: [Cat]+[PtCl4]? and [Cat]+[PtCl6]?, which formally are counted among halometallate ionic liquids, however, due to their high melting points they should be classified into anionic platinum complexes rather than into ionic liquids. All the derivatives were isolated and characterized spectroscopically (NMR, ESI-MS)and crystallographic structures were determined for three derivatives: ([BMPy]2[PtCl4], [BMIM]2[PtCl6]and [BMMIM]2[PtCl6]. Moreover, their melting points were measured and thermal stability was assessed. The above derivatives were employed as catalysts for hydrosilylation of olefins with diverse properties. All the studied catalysts showed high activity and their insolubility in the reaction medium made easy their isolation and multiple use in subsequent catalytic runs. The most effective catalysts did not lose their activity even after ten runs, thereby they make a very good alternative to commonly used homogeneous catalysts. Their simple synthesis and stability make them interesting both for economic and ecological reasons.
- Jankowska-Wajda, Magdalena,Bartlewicz, Olga,Walczak, Anna,Stefankiewicz, Artur R.,Maciejewski, Hieronim
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- The effect of the morpholinium ionic liquid anion on the catalytic activity of Rh (or Pt) complex-ionic liquid systems in hydrosilylation processes
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Studies were performed on the catalytic activity for olefin hydrosilylation shown by three rhodium complexes, [{Rh(μ-OSiMe3)(cod)}2] (I), [{Rh(μ-Cl)(cod)}2] (II) and [RhCl(PPh3)3] (III), and three platinum complexes, [Pt(PPh3)4] (IV), [Pt(PPh3)2Cl2] (V) and PtCl4 (VI), immobilized in a series of different anion-containing morpholinium ionic liquids. The effect of the kind of anion (its nucleophilic character) on the activity, stability and possibility of a catalytic system with multiple uses in the hydrosilylation process has been established. In the case of the best systems it was possible to reuse the same catalyst sample 10 times almost without any decrease in the activity and a TON value over 99?000 was obtained.
- Jankowska-Wajda, Magdalena,D?bek, Izabela,Fiedorow, Ryszard,Maciejewski, Hieronim
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- A family of rhodium(i) NHC chelates featuring O-containing tethers for catalytic tandem alkene isomerization-hydrosilylation
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The rhodium complex Rh(HL)(COD)Cl, 1, L being a functionalized N-heterocyclic carbene (NHC) ligand with an oxygen-containing pendant arm, has been used as the entry point to synthesize a series of neutral and cationic Rh(i) O,C chelates. While the Rh-carbene interaction is similar in all these 16-electron complexes, structural analysis reveals that the strength of the Rh-O bond is greatly affected by the nature of the O-donor: R-O- > R-OH > R-OBF3. These subtle changes in the nature of the O-containing tether are found to be responsible for large differences in the alkene hydrosilylation catalytic activity of these compounds: the stronger the Rh-O interaction, the better the catalytic performances. The most active catalyst, [Rh(L)(COD)], 2, demonstrated good catalytic activity under mild reaction conditions for the hydrosilylation of a range of alkene substrates with the industrially relevant non-activated tertiary silane, 1,1,1,3,5,5,5-heptamethyltrisiloxane (MDHM). Furthermore, this complex is an effective catalyst for the selective remote functionalization of internal olefins at room temperature via tandem alkene isomerization-hydrosilylation.
- Srivastava, Ravi,Jakoobi, Martin,Thieuleux, Chloé,Quadrelli, Elsje Alessandra,Camp, Clément
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p. 869 - 879
(2021/02/03)
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- Accelerated Anti-Markovnikov Alkene Hydrosilylation with Humic-Acid-Supported Electron-Deficient Platinum Single Atoms
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The hydrosilylation reaction is one of the largest-scale applications of homogeneous catalysis, and Pt homogeneous catalysts have been widely used in this reaction for the commercial manufacture of silicon products. However, homogeneous Pt catalysts result in considerable problems, such as undesired side reactions, unacceptable catalyst residues and disposable platinum consumption. Here, we synthesized electron-deficient Pt single atoms supported on humic matter (Pt1@AHA_U_400), and the catalyst was used in hydrosilylation reactions, which showed super activity (turnover frequency as high as 3.0×107 h?1) and selectivity (>99 %). Density functional theory calculations reveal that the high performance of the catalyst results from the atomic dispersion of Pt and the electron deficiency of the Pt1 atoms, which is different from conventional Pt nanoscale catalysts. Excellent performance is maintained during recycle experiments, indicating the high stability of the catalyst.
- Antonietti, Markus,Badamdorj, Bolortuya,Janik, Michael J.,Liu, Kairui,Yang, Fan
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supporting information
p. 24220 - 24226
(2021/10/07)
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- NOVEL ISOCYANIDE COMPOUND, FORMAMIDE COMPOUND, AND METHOD FOR PRODUCING ORGANIC SILICON COMPOUND USING ISOCYANIDE COMPOUND
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To provide a novel isocyanide compound.SOLUTION: The present disclosure provides an isocyanide compound represented by the formula (1). CN-CR1R2-SiR(3-a) (OSiR3R4R5)a (1) [where R1, R2, R3, R4, R5 and R independently represent a hydrogen atom, OR' (R' is a hydrogen atom or an unsubstituted or substituted C1-30 monovalent hydrocarbon group), or an unsubstituted or substituted C1-30 monovalent hydrocarbon group, optionally involving one or more atoms selected from oxygen, nitrogen, sulfur and phosphorus, a is an integer of 1-3].SELECTED DRAWING: Figure 2
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Paragraph 0101
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- The two faces of platinum hydrospirophosphorane complexes—Not only relevant catalysts but cytotoxic compounds as well
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Platinum complexes [PtCl2(L)] L = L1, L2 with symmetrical HP (OCH2CMe2NH)2 (L1) and unsymmetrical HP(OCMe2CMe2O)(OCH2CMe2NH) (L2) hydrospirophosphorane (HSP) ligands were demonstrated to play a dual role of catalysts and cytotoxic compounds as well. The structure of new complex [PtCl2(L2)] was confirmed by physicochemical and spectroscopic methods, as well as single X-ray diffraction studies for [PtCl2{P (OCMe2CMe2O)(OCH2CMe2NH2)}]. HSP ligand coordinated to the platinum center in bidentate κ2-P,NH2 chelating mode of fashion. Both complexes were found to exhibit catalytic activity for Heck cross-coupling reactions of iodobenzene with substituted styrenes, with good conversion and yield of stilbenes. Moreover, complexes have been applied as excellent catalysts for highly regioselective hydrosilylation of aromatic and aliphatic terminal olefins, and acetylenes terminal and internal as well. On the other hand, the preliminary biological studies revealed that in the presence of foretinib, drug candidate in clinical trials for the treatment of cancer, platinum complexes revealed increased synergistic effect and efficiently decreased the number of viable cells of triple negative breast cancer MDA-MB-231 cell line.
- Augustyniak, Adam W.,Kowalczyk, Marta,Majchrzak, Mariusz,Nowak, Dorota,Pi?tka, Marta,Siczek, Mi?osz,Simiczyjew, Aleksandra,Skar?yńska, Anna,W?odarczyk, Kinga
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- Platinum and rhodium complexes ligated by imidazolium-substituted phosphine as efficient and recyclable catalysts for hydrosilylation
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Phosphine ligands functionalized with imidazolium salt were prepared and used for the synthesis of two new ionic Pt(0) complexes and four Rh(i) complexes. The catalysts show very good catalytic activity in hydrosilylation reaction of olefins of different polarities (1-octene and allyl glycidyl ether) with 1,1,1,3,5,5,5-heptamethyltrisiloxane. Their insolubility in the reaction medium facilitated their isolation and permitted their multiple use in subsequent catalytic runs. In hydrosilylation of nonpolar olefins, all the catalysts showed similar activity, while in hydrosilylation of polar olefins the catalysts containing the bromide anion showed higher activity. The results permitted identification of the most effective catalysts for hydrosilylation of olefins of different polarities. The most active complexes did not lose their activity even after 10 catalytic runs, thereby providing a very good alternative to the commonly used homogeneous catalysts.
- Jankowska-Wajda, Magdalena,Bartlewicz, Olga,Szpecht, Andrea,Zajac, Adrian,Smiglak, Marcin,MacIejewski, Hieronim
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p. 29396 - 29404
(2019/09/30)
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- Tuning the redox non-innocence of a phenalenyl ligand toward efficient nickel-assisted catalytic hydrosilylation
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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.
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p. 2817 - 2825
(2018/03/21)
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- Fe and Co Complexes of Rigidly Planar Phosphino-Quinoline-Pyridine Ligands for Catalytic Hydrosilylation and Dehydrogenative Silylation
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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.
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p. 2760 - 2768
(2018/09/10)
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- Highly selective hydrosilylation of olefins and acetylenes by platinum(0) complexes bearing bulky N-heterocyclic carbene ligands
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Platinum complexes bearing bulky N-heterocyclic carbene (NHC) ligands, i.e., [Pt(IPr?)(dvtms)] (where, IPr? = 1,3-bis{2,6-bis(diphenylmethyl)-4-methylphenyl}imidazol-2-ylidene) and [Pt(IPr?OMe)(dvtms)] (where, IPr?OMe = 1,3-bis{2,6-bis(diphenylmethyl)-4-m
- Zak,Bo?t,Kubicki,Pietraszuk
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supporting information
p. 1903 - 1910
(2018/02/17)
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- Highly-active, graphene-supported platinum catalyst for the solventless hydrosilylation of olefins
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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
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supporting information
p. 13343 - 13346
(2018/12/13)
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- HYDROSILYLATION REACTION CATALYST
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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 a carbine compound such as 1,3-dimesitylimidazol-2-ylidene, etc. 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.
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- DEHYDROGENATIVE SILYLATION, HYDROSILYLATION AND CROSSLINKING USING PYRIDINEDIIMINE COBALT CARBOXYLATE CATALYSTS
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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.
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Page/Page column 34; 35
(2017/02/24)
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- HYDROSILYLATION REACTION CATALYST
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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.
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Paragraph 0224-0225; 0234-0235
(2017/12/27)
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- Conversion of alkanes to linear alkylsilanes using an iridium-iron-catalysed tandem dehydrogenation-isomerization-hydrosilylation
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The conversion of inexpensive, saturated hydrocarbon feedstocks into value-added speciality chemicals using regiospecific, catalytic functionalization of alkanes is a major goal of organometallic chemistry. Linear alkylsilanes represent one such speciality chemical - they have a wide range of applications, including release coatings, silicone rubbers and moulding products. Direct, selective, functionalization of alkanes at primary C-H bonds is difficult and, to date, methods for catalytically converting alkanes into linear alkylsilanes are unknown. Here, we report a well-defined, dual-catalyst system for one-pot, two-step alkane silylations. The system comprises a pincer-ligated Ir catalyst for alkane dehydrogenation and an Fe catalyst that effects a subsequent tandem olefin isomerization-hydrosilylation. This method exhibits exclusive regioselectivity for the production of terminally functionalized alkylsilanes. This dual-catalyst strategy has also been applied to regioselective alkane borylations to form linear alkylboronate esters.
- Jia, Xiangqing,Huang, Zheng
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p. 157 - 161
(2016/02/03)
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- Ionic liquids as solvents for rhodium and platinum catalysts used in hydrosilylation reaction
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A group of imidazolium and pyridinium based ionic liquids has been synthetized, and their ability to dissolve and activate the catalysts used in hydrosilylation reaction of 1-octane and 1,1,1,3,5,5,5-heptamethyltrisiloxane was investigated. An organometallic catalyst as well as inorganic complexes of platinum and rhodium dissolved in ionic liquids were used, forming liquid solutions not miscible with the substrates or with the products of the reaction. The results show that application of such a simple biphasic catalytic system enables reuse of ionic liquid phase with catalysts in multiple reaction cycles reducing the costs and decreasing the amount of catalyst needed per mole of product.
- Zielinski, Witold,Kukawka, Rafal,Maciejewski, Hieronim,Smiglak, Marcin
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- Bench-Stable, Substrate-Activated Cobalt Carboxylate Pre-Catalysts for Alkene Hydrosilylation with Tertiary Silanes
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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.
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p. 2632 - 2636
(2016/04/26)
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- Non-Precious-Metal Catalytic Systems Involving Iron or Cobalt Carboxylates and Alkyl Isocyanides for Hydrosilylation of Alkenes with Hydrosiloxanes
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A mixture of an iron or a cobalt carboxylate and an isocyanide ligand catalyzed the hydrosilylation of alkenes with hydrosiloxanes with high efficiency (TON >103) and high selectivity. The Fe catalyst showed excellent activity for hydrosilylation of styrene derivatives, whereas the Co catalyst was widely effective in reaction of alkenes. Both of them catalyzed the reaction with allylic ethers. Chemical modification and cross-linking of silicones were achieved by choosing the right catalyst and reaction conditions.
- Noda, Daisuke,Tahara, Atsushi,Sunada, Yusuke,Nagashima, Hideo
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supporting information
p. 2480 - 2483
(2016/03/12)
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- NOVEL CATALYSTS HAVING A SILENE LIGAND
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A subject matter of the present invention is the use as catalyst, in particular in hydrosilylation, of a metal complex including at least one metal atom chosen from the metals of Groups 8, 9 and 10 of the Periodic Table of the Elements and one or more lig
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Paragraph 0215; 0216; 0217; 0218; 0219
(2016/06/13)
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- LIGAND COMPONENTS, ASSOCIATED REACTION PRODUCTS, ACTIVATED REACTION PRODUCTS, HYDROSILYLATION CATALYSTS AND HYDROSILYLATION CURABLE COMPOSITIONS INCLUDING THE LIGAND COMPONENTS, AND ASSOCIATED METHODS FOR PREPARING SAME
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A ligand component is formed according to formula (1 ):R 12P-X-N=C(R2)-Y, wherein R1 is Ph or Cyc or a C1-C20 substituted or unsubstituted ailkyl group; each Ph is a substituted or unsubsti
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Paragraph 00193-00194; 00205-00206
(2016/07/05)
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- A Highly Chemoselective Cobalt Catalyst for the Hydrosilylation of Alkenes using Tertiary Silanes and Hydrosiloxanes
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The hydrosilylation of alkene substrates bearing additional functionalities is difficult to achieve using earth-abundant catalysts and has not been extensively realized with both earth-abundant transition metals and tertiary silanes or hydrosiloxanes. Reported herein is a well-defined bis(carbene) cobalt(I)-dinitrogen complex for the efficient, catalytic anti-Markovnikov hydrosilylation of terminal alkenes, featuring a broad substrate scope. Alkenes containing hydroxyl, amino, ester, epoxide, ketone, formyl, and nitrile groups are selectively hydrosilylated in this reaction sequence. Multinuclear NMR studies of reactive intermediates gave insights into the mechanism.
- Ibrahim, Abdulrahman D.,Entsminger, Steven W.,Zhu, Lingyang,Fout, Alison R.
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p. 3589 - 3593
(2016/07/06)
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- NOVEL CATALYSTS WITH A SILYLENE LIGAND
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A metal complex including at least one metal atom chosen from the metals of Groups 8, 9 and 10 of the Periodic Table of the Elements and one or more ligands, wherein at least one ligand includes a cyclic silylene structure and a Lewis base which donates a
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Paragraph 0226; 0227; 0228; 0229;
(2016/07/05)
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- Method for preparing carbene in solution, novel stable form of carbene obtained in particular by means of said method, and uses thereof in catalysis
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The invention relates to a method for preparing carbene by means of deprotonation of a precursor salt using a strong base. A purpose of the invention is to enhance the synthesis of carbenes, i.e. to simplify same, to make said synthesis more economical an
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Page/Page column 15
(2016/12/16)
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- METHOD FOR PRODUCING ORGANOSILICON COMPOUND AND CATALYST COMPOSITION
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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
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Paragraph 0031; 0032
(2016/12/01)
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- User-Friendly Platinum Catalysts for the Highly Stereoselective Hydrosilylation of Alkynes and Alkenes
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With a view to addressing the shortcomings of traditional catalysts, a new generation of outstanding N- heterocyclic carbene platinum(0) complexes for the hydrosilylation of unsaturated carbon-carbon bonds is reported. Their discovery and application to the stereoselective addition of various silanes to silylated alkynes, terminal acetylenes, and olefins is presented. Insights into the catalytic cycle and the origin of the stereoselectivity are also discussed.
- Dierick, Steve,Vercruysse, Emilie,Berthon-Gelloz, Guillaume,Mark?, István E.
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supporting information
p. 17073 - 17078
(2015/11/16)
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- MONONUCLEAR IRON COMPLEX AND ORGANIC SYNTHESIS REACTION USING SAME
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Provided is a mononuclear iron complex that comprises an iron-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound. In formula (1), R 1 -R 6 either independently represent an alkyl group, an aryl group, an aralkyl group or the like that may be substituted with a hydrogen atom or X, or represent a crosslinking substituent in which at least one pair comprising one of R 1 -R 3 and one of R 4 -R 6 is combined. X represents a halogen atom, an organoxy group, or the like. L represents a two-electron ligand other than CO. When a plurality of L are present, the plurality of L may be the same as or different from each other. When two L are present, the two L may be bonded to each other. n and m independently represent an integer of 1 to 3 with the stipulation that n+m equals 3 or 4.
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Paragraph 0195-0197
(2016/12/01)
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- METHOD FOR PREPARING CARBENE IN SOLUTION, NOVEL STABLE FORM OF CARBENE OBTAINED IN PARTICULAR BY MEANS OF SAID METHOD, AND USES THEREOF IN CATALYSIS
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The invention relates to a method for preparing carbene by means of deprotonation of a precursor salt using a strong base. A purpose of the invention is to enhance the synthesis of carbenes, i.e. to simplify same, to make said synthesis more economical an
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Paragraph 0235-0238
(2017/01/02)
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- MONONUCLEAR RUTHENIUM COMPLEX AND ORGANIC SYNTHESIS REACTION USING SAME
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Provided is a mononuclear ruthenium complex that comprises a ruthenium-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound. In formula (1), R 1 -R 6 either independently represent an alkyl group, an aryl group, an aralkyl group or the like that may be substituted with a hydrogen atom or X, or represent a crosslinking substituent in which at least one pair comprising one of R 1 -R 3 and one of R 4 -R 6 is combined. X represents a halogen atom, an organoxy group, or the like. L represents a two-electron ligand other than CO and phosphine. When a plurality of L are present, the plurality of L may be the same as or different from each other. When two L are present, the two L may be bonded to each other. n and m independently represent an integer of 1 to 3 with the stipulation that n+m equals 3 or 4.
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Paragraph 0189-0190; 0195
(2017/01/02)
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- Dehydrogenative Silylation and Crosslinking Using Cobalt Catalysts
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Disclosed herein are cobalt complexes containing terdentate pyridine di-imine ligands and their use as efficient and selective dehydrogenative silylation and crosslinking catalysts.
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Paragraph 0105
(2014/03/24)
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- Non-precious Metal-based Hyrdosilylation Catalysts Exhibiting Improved Selectivity
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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.
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Paragraph 0104
(2013/06/28)
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- Phosphinite-iminopyridine iron catalysts for chemoselective alkene hydrosilylation
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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
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supporting information
p. 19154 - 19166
(2014/01/17)
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- SATURATED N-HETEROCYCLIC CARBENE-LIGAND METAL COMPLEX DERIVATIVES, PREPARING METHOD THEREOF, AND PREPARING METHOD OF SILANE COMPOUND BY HYDROSILYLATION REACTION USING THE SAME AS CATALYST
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Provided are a saturated N-heterocyclic carbene-ligand metal complex derivative, a method for preparing the same, and a method for preparing a silane compound by hydrosilylation using the same as a catalyst. To describe in more detail, the metal complex derivative has a saturated N-heterocyclic carbene derivative and an olefin ligand at the same time. A silane compound is prepared by hydrosilylation in the presence of the metal complex derivative as a catalyst. The provided metal complex derivative of the present invention has superior stability during hydrosilylation reaction and is capable of effectively performing the hydrosilylation reaction at low temperature even with small quantity. Further, a product with superior regioselectivity may be obtained. In addition, after the hydrosilylation reaction is completed, the metal complex derivative may be recovered and recycled.
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Page/Page column 19-20
(2011/07/30)
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- Pyrylium sulfonate based ionic liquids
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Pyrylium salts represent a new group of ionic liquids (ILs) containing a positive charge on the oxygen atom. The novel ILs were obtained starting with 4-pyrones from petroleum feedstock and renewable resources and sulfonic acids. The use of carboxylic aci
- Pernak, Juliusz,Swierczynska, Anna,Kot, Mariusz,Walkiewicz, Filip,MacIejewski, Hieronim
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supporting information; experimental part
p. 4342 - 4345
(2011/09/12)
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- HYDROSILYLATION CATALYSTS
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Disclosed herein are manganese, iron, cobalt, or nickel complexes containing terdentate pyridine diimine ligands and their use as efficient and selective hydrosilylation catalysts.
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Page/Page column 24-25
(2011/02/24)
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- Synthesis and structural characterization of new chiral (biscarbene)platinum(II) complexes
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New chiral bis(triazolium) salts have been prepared in good yields. The corresponding mononuclear platinum(II) complexes [Pt{bis(NHC)}X2] (X = Br, I) have been synthesized and spectroscopically characterized. One of the synthesized biscarbene c
- Riederer, Stephanie K. U.,Bechlars, Bettina,Herrmann, Wolfgang A.,Kuehn, Fritz E.
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experimental part
p. 249 - 254
(2011/04/14)
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- SATURATED N-HETEROCYCLIC CARBENE-LIGAND METAL COMPLEX DERIVATIVES, PREPARING METHOD THEREOF, AND PREPARING METHOD OF SILANE COMPOUND BY HYDROSILYLATION REACTION USING THE SAME AS CATALYST
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Provided are a saturated N-heterocyclic carbene-ligand metal complex derivative, a method for preparing the same, and a method for preparing a silane compound by hydrosilylation using the same as a catalyst. To describe in more detail, the metal complex derivative has a saturated N-heterocyclic carbene derivative and an olefin ligand at the same time. A silane compound is prepared by hydrosilylation in the presence of the metal complex derivative as a catalyst. The provided metal complex derivative of the present invention has superior stability during hydrosilylation reaction and is capable of effectively performing the hydrosilylation reaction at low temperature even with small quantity. Further, a product with superior regioselectivity may be obtained. In addition, after the hydrosilylation reaction is completed, the metal complex derivative may be recovered and recycled.
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Page/Page column 11
(2011/07/08)
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- Fixed-Bed Hydrosilylation Catalyst Complexes and Related Methods
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The invention includes a fixed-bed catalyst complex that includes (i) a metal carbene catalyst, wherein the metal is platinum, and (ii) a catalyst support that includes one or more of silica, alumina and/or glass. The invention provides a fixed-bed catalyst complex that includes a catalyst complex including a carbene chosen from those represented by at least one of Formulae (I), (II), (III), and (IV): Where the vales of X and R1 to R7 are specifically defined. The complex also includes a catalyst support that comprises silica, related reaction products, and related reaction systems.
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Page/Page column 5
(2010/12/29)
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- Synthetic and structural studies of NHC-Pt(dvtms) complexes and their application as alkene hydrosilylation catalysts (NHC = N-heterocyclic carbene, dvtms = divinyltetramethylsiloxane)
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The synthesis and structural characterization of a series of platinum complexes, bearing N-heterocyclic carbenes (NHC) and divinyltetramethylsiloxane (dvtms) as supporting ligands, are described. The reaction of commercially available Karstedt's catalyst
- Berthon-Gelloz, Guillaume,Buisine, Olivier,Brière, Jean-Fran?ois,Michaud, Guillaume,Stérin, Sébastien,Mignani, Gérard,Tinant, Bernard,Declercq, Jean-Paul,Chapon, David,Markó, István E.
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p. 6156 - 6168
(2007/10/03)
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- Highly active and selective platinum(0)-carbene complexes. Efficient, catalytic hydrosilylation of functionalised olefins
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Readily available N-heterocyclic platinum-carbene complexes 1 are highly efficient catalysts for the regioselective hydrosilylation of alkenes. These novel organometallics tolerate a wide range of functional and protecting groups, can be stored for prolonged periods of time and are particularly active (TON > 106).
- Marko, Istvan E.,Sterin, Sebastien,Buisine, Olivier,Berthon, Guillaume,Michaud, Guillaume,Tinant, Bernard,Declercq, Jean-Paul
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p. 1429 - 1434
(2007/10/03)
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