17955-88-3Relevant academic research and scientific papers
Silacyclopropylideneplatinum(0) Complex as a Robust and Efficient Hydrosilylation Catalyst
Troadec, Thibault,Prades, Amparo,Rodriguez, Ricardo,Mirgalet, Raphael,Baceiredo, Antoine,Saffon-Merceron, Nathalie,Branchadell, Vicen?,Kato, Tsuyoshi
, p. 8234 - 8240 (2016)
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
The effect of the catalyst and the type of ionic liquid on the hydrosilylation process under batch and continuous reaction conditions
Jankowska-Wajda,Kukawka,Smiglak,Maciejewski
, p. 5229 - 5236 (2018)
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
Decoding catalytic activity of platinum carbene hydrosilylation catalysts
Meister, Teresa K.,Kück, Jens W.,Riener, Korbinian,P?thig, Alexander,Herrmann, Wolfgang A.,Kühn, Fritz E.
, p. 157 - 166 (2016)
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
A Dialkylsilylene-Pt(0) Complex with a DVTMS Ligand for the Catalytic Hydrosilylation of Functional Olefins
Iimura, Tomohiro,Akasaka, Naohiko,Iwamoto, Takeaki
, p. 4071 - 4076 (2016)
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.
Developing a Highly Active Catalytic System Based on Cobalt Nanoparticles for Terminal and Internal Alkene Hydrosilylation
Jakoobi, Martin,Dardun, Vincent,Veyre, Laurent,Meille, Valérie,Camp, Clément,Thieuleux, Chloé
, p. 11732 - 11740 (2020)
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.
Alkene Hydrosilylation Using Tertiary Silanes with α-Diimine Nickel Catalysts. Redox-Active Ligands Promote a Distinct Mechanistic Pathway from Platinum Catalysts
Pappas, Iraklis,Treacy, Sean,Chirik, Paul J.
, p. 4105 - 4109 (2016)
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.
Iron catalysts for selective anti-Markovnikov alkene hydrosilylation using tertiary silanes
Tondreau, Aaron M.,Atienza, Crisita Carmen Hojilla,Weller, Keith J.,Nye, Susan A.,Lewis, Kenrick M.,Delis, Johannes G. P.,Chirik, Paul J.
, p. 567 - 570 (2012)
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.
Second generation N-heterocyclic carbene-Pt(0) complexes as efficient catalysts for the hydrosilylation of alkenes
Buisine, Olivier,Berthon-Gelloz, Guillaume,Briere, Jean-Francois,Sterin, Sebastien,Mignani, Gerard,Branlard, Paul,Tinant, Bernard,Declercq, Jean-Paul,Marko, Istvan E.
, p. 3856 - 3858 (2005)
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.
New approach to hydrosilylation reaction in ionic liquids as solvent in microreactor system
Kukawka,Pawlowska-Zygarowicz,Dutkiewicz,Maciejewski,Smiglak
, p. 61860 - 61868 (2016)
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.
A general protocol for the synthesis of Pt-NHC (NHC = N-heterocyclic carbene) hydrosilylation catalysts
Maliszewski, Benon P.,Tzouras, Nikolaos V.,Guillet, Sébastien G.,Saab, Marina,Beli?, Marek,Van Hecke, Kristof,Nahra, Fady,Nolan, Steven P.
, p. 14673 - 14679 (2020)
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
