- Bis(2-thienyl)silanes: new, versatile precursors to arylsilanediols
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Silanediols have been shown to be effective bioisosteres for the hydrated carbonyl group. Current methods for the formation of silanediols place a number of constraints on how and where this functionality may be used. A range of arylsilanes that would allow both the formation of arylsilanediols and that are also compatible with multi-step synthetic routes, have been investigated as possible precursors to silanediols. Through this study bis(2-furyl)silanes and, in particular, bis(2-thienyl)silanes have been identified as practical precursors to arylsilanediols.
- Anderson, Thomas F.,Statham, Matthew A.J.,Carroll, Michael A.
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- Regioselective hydrosilylation of olefins catalyzed by co-iminobipyridine complexes: The role of cyclohexyl substituent on the imino nitrogen
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Regioselective hydrosilylation of aliphatic olefins catalyzed by Co-iminobipyridine complexes, CoRa, were investigated, where R indicates a substituent on the imino nitrogen in an iminobipyridine ligand (iminobypyridine = [2,2¤-bpy]-6-C(Me)=N-R). Synthese
- Kobayashi, Katsuaki,Moriuchi, Toshiyuki,Nakazawa, Hiroshi,Taguchi, Daisuke
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p. 1086 - 1094
(2020/11/09)
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- Titanium-catalyzed hydrosilylation of olefins: A comparison study on Cp2TiCl2/Sm and Cp2TiCl2/LiAlH4 catalyst system
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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
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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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- Hydrosilylation of Olefins Catalyzed by Iron Complexes Bearing Ketimine-Type Iminobipyridine Ligands
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A series of NNN-pincer iron complexes bearing ketimine-type iminobipyridene (BPI) ligands were prepared. These iron complexes were effective catalysts for the hydrosilylation of olefins using primary, secondary, and tertiary silanes. The effect of the substituents on the imino carbon on the catalytic activity was examined, and it was found that an appropriate combination of the imino carbon and imino nitrogen substituents led to complexes with quite high catalytic activity: the turnover number achieved was up to 42000. These iron catalytic systems provide a low-cost and promising alternative to currently employed precious metal systems for the hydrosilylation of olefins.
- Toya, Yuki,Hayasaka, Kazumasa,Nakazawa, Hiroshi
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p. 1727 - 1735
(2017/05/15)
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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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- Well-defined NHC-rhodium hydroxide complexes as alkene hydrosilylation and dehydrogenative silylation catalysts
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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.
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p. 270 - 276
(2013/02/25)
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- Highly regioselective rhenium-catalyzed hydrosilylation of styrenes
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The addition reaction of silanes to styrenes is efficiently catalyzed by ReBr(CO)5 in toluene heated at 120°C and selectively affords anti-Markovnikov adducts in good to high yields. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Zhao, Wen-Guo,Hua, Ruimao
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p. 5495 - 5498
(2008/02/04)
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