- Mononuclear ruthenium complex and organic synthesis reaction using same
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A neutral or cationic mononuclear ruthenium divalent complex represented by formula (1) can actualize exceptional catalytic activity in at least one reaction among a hydrosilylation reaction, hydrogenation reaction, and carbonyl compound reduction reaction. (In the formula, R1-R6 each independently represent a hydrogen atom or an alkyl group, aryl group, aralkyl group, organooxy group, monoorganoamino group, diorganoamino group, monoorganophosphino group, diorganophosphino group, monoorganosilyl group, diorganosilyl group, triorganosilyl group, or organothio group optionally substituted by X; at least one pair comprising any of R1-R3 and any of R4-R6 together represents a crosslinkable substituent; X represents a halogen atom, organooxy group, monoorganoamino group, diorganoamino group, or organothio group; L each independently represent a two-electron ligand other than CO and thiourea ligands; two L may bond to each other; and m represents an integer of 3 or 4.)
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Paragraph 34; 35; 36; 37
(2018/03/26)
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- Cobalt(0) and Iron(0) Isocyanides as Catalysts for Alkene Hydrosilylation with Hydrosiloxanes
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Iron and cobalt isocyanides, Fe(CNR)5 (1) and Co2(CNR)8 (2), where R = t-butyl (tBu), adamantyl (Ad), and mesityl (Mes), were prepared by reduction of FeBr2 or CoI2 in the presence of CNR by C8K or silica-Na. These complexes were subjected to catalytic hydrosilylation of alkenes with hydrosiloxanes, and the results are compared with those obtained by previously reported Fe(OPiv)2/CNAd or Co(OPiv)2/CNAd catalyst systems. Hydrosilylation of allylic ethers with 1,1,1,3,3-pentamethyldisiloxane (PMDS) catalyzed by 1 and the reaction of several alkenes with PMDS or 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD′M) catalyzed by 2 exhibited greater catalytic activity than that observed for the Fe(OPiv)2 or Co(OPiv)2/CNR catalyst system. Complexes 1 and 2 were effective for catalytic chemical modification of silicone fluids containing Si-H groups and for two-component silicone curing. In all cases, selectivity of the reaction in terms of formation of the desired product by hydrosilylation and of byproducts due to dehydrogenative silylation did not differ between the metal isocyanide complexes and the corresponding M(OPiv)2/CNR catalyst system. Catalytically active species generated from 1, 2, and the M(OPiv)2/CNR catalyst system were also investigated.
- Sanagawa, Atsushi,Nagashima, Hideo
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supporting information
p. 2859 - 2871
(2018/09/12)
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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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- METHOD FOR PRODUCING ORGANOSILICON COMPOUND BY HYDROSILYLATION REACTION USING PLATINUM-SUPPORTING CATALYST
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PROBLEM TO BE SOLVED: To develop a heterogeneous catalyst useful for a hydrosilylation reaction of alkenes and alkynes, and provide a new method for producing an organosilicon compound using the hydrosilylation reaction. SOLUTION: In a hydrosilylation reaction of alkenes and alkynes, a platinum-supporting catalyst with platinum particles having an average particle size of 2.0-5.0 nm, is used, so that an organosilicon compound can be efficiently produced. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0040
(2018/09/27)
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- Cobalt Catalysts for Alkene Hydrosilylation under Aerobic Conditions without Dry Solvents or Additives
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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
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supporting information
p. 4867 - 4874
(2018/11/25)
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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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- 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
(2017/12/27)
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- HYDROSILYLATION IRON CATALYST
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A hydrosilylation iron catalyst prepared from a two-electron ligand (L) and a mononuclear, binuclear, or trinuclear complex of iron indicated by formula (1), Fe having bonds with carbon atoms included in X and the total number of Fe-carbon bonds being 2-10. As a result of using iron, the hydrosilylation iron catalyst is advantageous from a cost perspective as well as being easily synthesized. Hydrosilylation reactions can be promoted under mild conditions by using this catalyst. [in-line-formulae]Fe(X)a??(1)[/in-line-formulae] (in the formula, each X independently indicates a C2-30 ligand that may include an unsaturated group excluding carbonyl groups (CO groups) and cyclopentadienyl groups, however at least one X includes an unsaturated group, a indicates an integer of 2-4 per Fe atom.)
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Paragraph 0197; 0228-0233; 0262; 0270; 0292-0294; 0299-0300
(2017/09/25)
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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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- 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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- 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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p. 4105 - 4109
(2016/07/12)
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- Combinatorial Approach to the Catalytic Hydrosilylation of Styrene Derivatives: Catalyst Systems Composed of Organoiron(0) or (II) Precursors and Isocyanides
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(COT)2Fe and the open ferrocenes (MPDE)2Fe (MPDE = η5-3-methylpentadienyl) and (DMPDE)2Fe (DMPDE = η5-2,4-dimethylpentadienyl) were found to function as catalyst precursors for the hydrosilylation of alkenes in the presence of auxiliary ligands. Screening trials determined that the optimal catalyst system was composed of (COT)2Fe and adamantyl isocyanide, allowing the selective hydrosilylation of styrene derivatives with trisubstituted hydrosiloxanes and a polydimethylsiloxane bearing Me2SiH moieties as the end groups. Under the appropriate conditions, the dehydrogenative silylation side reaction was completely suppressed, and the reaction TON exceeded 5000. (Chemical Equation Presented).
- Sunada, Yusuke,Noda, Daisuke,Soejima, Hiroe,Tsutsumi, Hironori,Nagashima, Hideo
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supporting information
p. 2896 - 2906
(2015/06/30)
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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 0192-0194
(2016/12/01)
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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 0186-0187; 0195
(2017/01/02)
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