Recent advances and actual challenges in late transition metal catalyzed hydrosilylation of olefins from an industrial point of view

Troegel, Dennis; Stohrer, Jürgen

doi:10.1016/j.ccr.2010.12.025

Cited by 560 publications

(406 citation statements)

References 87 publications

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“…Heat has been the most commonly used trigger in industrial applications so far. Various examples of thermally activated hydrosilylation have already been covered in the review by Troegel and Stohrer [6], where various inhibitors of platinum catalysts, platinum catalysts containing inhibiting ligands and encapsulated catalysts were described. In this review, advances in the field of non-thermally triggered hydrosilylation reactions will be described.…”

Section: Non-thermal Stimuli For Hydrosilylation Reactionsmentioning

confidence: 99%

“…Initial approaches towards photo-triggerable hydrosilylation reactions involved the photo-activation of various metal hexacarbonlys, namely Cr(CO) 6 , Mo(CO) 6 , Fe(CO) 6 and Ni(CO) 6 . However, these catalysts tend to agglomerate, are often non-selective, and only achieve mediocre degrees of conversions [76].…”

Section: Light-initiated Hydrosilylation Reactionsmentioning

confidence: 99%

“…1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since An iron-disilyl-dicarbonyl complex carrying a 1,2-bis(dimethylsilyl)benzyl ligand that (weakly) coordinated to the iron center in η 2 -(H-Si) was reported by Nagashima and coworkers [15]. This complex successfully catalyzed the hydrosilylation of alkenes (as well as the catalytic hydrogenation of alkenes and the hydrosilane-mediated reduction of carbonyl compounds).…”

Section: Introductionmentioning

confidence: 99%

“…Due to research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since Polymers 2017, 9, 534 2 of 37 research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively.…”

Section: Introductionmentioning

confidence: 99%

“…1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since Polymers 2017, 9, 534 2 of 37 research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since An iron-disilyl-dicarbonyl complex carrying a 1,2-bis(dimethylsilyl)benzyl ligand that (weakly) coordinated to the iron center in η 2 -(H-Si) was reported by Nagashima and coworkers [15].…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Fifty Years of Hydrosilylation in Polymer Science: A Review of Current Trends of Low-Cost Transition-Metal and Metal-Free Catalysts, Non-Thermally Triggered Hydrosilylation Reactions, and Industrial Applications

2017

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Hydrosilylation reactions, the (commonly) anti-Markovnikov additions of silanes to unsaturated bonds present in compounds such as alkenes and alkynes, offer numerous unique and advantageous properties for the preparation of polymeric materials, such as high yields and stereoselectivity. These reactions require to be catalyzed, for which platinum compounds were used in the initial stages. Celebrating the 50th anniversary of hydrosilylations in polymer science and, concomitantly, five decades of continuously growing research, hydrosilylation reactions have advanced to a level that renders them predestined for transfer into commercial products on the large scale. Facing this potential transfer, this review addresses and discusses selected current trends of the scientific research in the area, namely low-cost transition metal catalysts (focusing on iron, cobalt, and nickel complexes), metal-free catalysts, non-thermally triggered hydrosilylation reactions (highlighting stimuli such as (UV-)light), and (potential) industrial applications (highlighting the catalysts used and products manufactured). This review focuses on the hydrosilylation reactions involving alkene reactants.

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Section: Non-thermal Stimuli For Hydrosilylation Reactionsmentioning

confidence: 99%

Section: Light-initiated Hydrosilylation Reactionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since Polymers 2017, 9, 534 2 of 37 research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since An iron-disilyl-dicarbonyl complex carrying a 1,2-bis(dimethylsilyl)benzyl ligand that (weakly) coordinated to the iron center in η 2 -(H-Si) was reported by Nagashima and coworkers [15].…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Fifty Years of Hydrosilylation in Polymer Science: A Review of Current Trends of Low-Cost Transition-Metal and Metal-Free Catalysts, Non-Thermally Triggered Hydrosilylation Reactions, and Industrial Applications

2017

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Preparation of Diisopropylammonium Bis(catecholato)cyclohexylsilicate

et al. 2018

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Graphical Abstract Procedure A. Cyclohexyltrimethoxysilane (2)A 250 mL, oven-dried, two-necked, round-bottomed flask is charged with a 3.2 cm, Tefloncoated magnetic oval stir bar and coupled with a 50 mL dropping funnel. Both the dropping funnel and the round-bottomed flask are sealed with a rubber septum. The system is evacuated for 10 min and back-filled with nitrogen. This process is repeated twice more, and then, the flask is charged by syringe with pentane (180 mL), anhydrous pyridine (21.0 mL, 20.5 g, 260 mmol, 4 equiv), and anhydrous methanol (10.5 mL, 8.3 g, 260 mmol, 4 equiv) (Notes 1-3).Additionally, a solution of cyclohexyltrichlorosilane 1 (14.14 g, 65.0 mmol, 1.0 equiv) in pentane (37 mL) is prepared in an addition funnel. (Figure 1, left) The stirred, homogeneous solution (Note 4) is cooled to 0 °C (external temperature) via an ice-water bath while under a nitrogen atmosphere (Figure 1). After cooling for 10 min the solution in the dropping funnel is added dropwise to the flask over 35 min (Notes 5,6,and 7). A voluminous white 1 Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, PA 19104-6323. 2 Pyridine was purchased from Fisher scientific (Certified ACS grade, ≥99%) and stored over KOH pellets.1 The following reagents in this section were purchased from commercial sources and used without further purification: Pentane (≥99%, Acros Organics) and methanol (extra dry over 4 Å molecular sieves, 99.8%, Acros Organics). 3 Although pentane is used in this protocol, a number of other solvents can be used (e.g., n-hexane, n-heptane, diethyl ether, tetrahydrofuran) with similar results.. For simple aliphatic alkyltrichlorosilanes hydrocarbon solvents are favored because of ease of product isolation. 4 The solution is stirred at 500 rpm throughout the reaction. 5 The solution in the funnel has a milky color. Figure 1, right) forms upon addition of 1. Following complete addition of 1, the reaction mixture is stirred at 0 °C for 5 min. The ice bath is removed, and the heterogeneous solution is stirred for 3 h at room temperature. HHS Public AccessUpon confirmation that the reaction is complete by crude 1 H NMR, the stirring is stopped, and the solids are allowed to settle (Figure 2) (Note 8). The reaction mixture is decanted from the solid pyridinium hydrochloride and transferred to a 1000 mL separatory funnel (Note 9). The white pyridinium salt is washed with pentane (100 mL) to assist in transferring all of the product to the funnel. The separatory funnel is charged with deionized H 2 O (250 mL). The layers are separated, and the aqueous layer is extracted with pentane (2 × 125 mL). The combined organic layers are washed with 2 M aqueous HCl (2 × 100 mL), saturated aqueous NaHCO 3 (150 mL), deionized water (150 mL), and then saturated aqueous NaCl (150 mL). The organic layer is then dried over sodium sulfate (25 g), and after filtration, the solvent is removed in vacuo by rotary evaporation (Note 10) to furnish pure 2 (12.49 g, 94%)...

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Hydrogenation and Other Hydrogen‐Based Catalytic Reactions

Bhaduri¹,

Doble²

2014

Homogeneous Catalysis

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Recent advances and actual challenges in late transition metal catalyzed hydrosilylation of olefins from an industrial point of view

Cited by 560 publications

References 87 publications

Fifty Years of Hydrosilylation in Polymer Science: A Review of Current Trends of Low-Cost Transition-Metal and Metal-Free Catalysts, Non-Thermally Triggered Hydrosilylation Reactions, and Industrial Applications

Fifty Years of Hydrosilylation in Polymer Science: A Review of Current Trends of Low-Cost Transition-Metal and Metal-Free Catalysts, Non-Thermally Triggered Hydrosilylation Reactions, and Industrial Applications

Preparation of Diisopropylammonium Bis(catecholato)cyclohexylsilicate

Hydrogenation and Other Hydrogen‐Based Catalytic Reactions

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