Copper-Catalyzed Formic Acid Synthesis from CO<sub>2</sub> with Hydrosilanes and H<sub>2</sub>O

Motokura, Ken; Kashiwame, Daiki; Miyaji, Akimitsu; Baba, Toshihide

doi:10.1021/ol301034j

Cited by 159 publications

(79 citation statements)

References 37 publications

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“…Polymers 2017, 9, 534 25 of 37 CO2 to generate silanols and formic acid in a one-pot reaction ( Figure 41) [120]. The high yield of up to 95% and TONs of 8100, however, are counterbalanced by the high prices of hydrosilanes.…”

Section: High Efficient/low-cost Hydrosilylation (Solvent-free Conditmentioning

confidence: 99%

“…Scale-up experiments from 2 to 100 mmol substrate indicate no loss of selectivity or conversion degree at higher amounts. [123] Polymers 2017, 9, 534 25 of 37 CO2 to generate silanols and formic acid in a one-pot reaction ( Figure 41) [120]. The high yield of up to 95% and TONs of 8100, however, are counterbalanced by the high prices of hydrosilanes.…”

Section: High Efficient/low-cost Hydrosilylation (Solvent-free Conditmentioning

confidence: 99%

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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: High Efficient/low-cost Hydrosilylation (Solvent-free Conditmentioning

confidence: 99%

Section: High Efficient/low-cost Hydrosilylation (Solvent-free Conditmentioning

confidence: 99%

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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“…[1][2][3] A variety of catalysts have been discovered and developed for this reaction, including complexes of Co, 4 Cu, [5][6][7][8] Ir, [9][10][11][12][13][14] Ni, [15][16][17] Pd/Pt, 18 Rh, 19 Ru, [20][21][22][23][24][25] Sc, 26 Zn, [27][28][29] and Zr, 30 frustrated Lewis pairs, [31][32][33][34][35][36] organocatalysts, [37][38][39][40][41][42] alkali metal carbonates, 43 and even polar solvents such as DMF. 38 These reactions result in various reduction products including silyl-formates, -acetals, andethers, CO, and methane.…”

Section: Introductionmentioning

confidence: 99%

Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion

Morris

Weetman

Wennmacher

et al. 2017

Catal. Sci. Technol.

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aThe simple perrhenate salt [NĲhexyl) 4 ]ĳ(ReO 4 )] acts as a catalyst for the reduction of organic carbonyls and carbon dioxide by primary and secondary hydrosilanes. In the case of CO 2 , this results in the formation of methanol equivalents via silylformate and silylacetal intermediates. Furthermore, the addition of alkylamines to the reaction mixture favours catalytic amine N-methylation over methanol production under certain conditions. DFT analysis of the mechanism of CO 2 reduction shows that the perrhenate anion activates the silylhydride forming a hypervalent silicate transition state such that the CO 2 can directly cleave a Si-H bond. IntroductionThe hydrosilylation of CO 2 to silylformates and silylethers is an attractive route for CO 2 utilisation as, unlike hydrogenation, this reaction is exergonic due to the comparative ease of Si-H bond activation and the strength of the Si-O bond, and the availability of relatively inexpensive and environmentally benign hydrosilanes. 66 Important to this chemistry is the formation of a lipophilic ion pair in which electrostatic and hydrogen-bonding interactions are enhanced in the hydrophobic phase. This catalyst has the advantages of ease of synthesis and manipulation and lack of air-sensitivity, and the recovery of the precious metal is driven by straightforward reverse phase-transfer. Given the efficacy of this new catalyst system and the use of high oxidation state rhenium oxo complexes in reduction catalysis, it is shown here that perrhenate can act as a catalyst for the reduction of carbon dioxide to methanol equivalents by hydrosilanes, that the methylation of alkylamines using CO 2 as the C 1 source occurs under similar catalytic conditions, and that this method can be used to reduce aldehydes and ketones to silylalcohols. Results and discussion Reduction of carbon dioxideInitially, the reaction between CO 2 (2.5 bar), PhSiH 3 (2.0 mmol), and pyridinium perrhenate 1 (2.0 mol%) at 80°C in C 6 D 6 in a Teflon-tapped NMR tube was monitored by 1 H NMR spectroscopy. However, only 15% consumption of hydrosilane is seen under these conditions after 16 h ( Fig. S2 and S3, ESI †). In contrast, when the reaction is carried out using the simple lipophilic quaternary ammonium salt [NĲhexyl) 4 ]ĳReO 4 ] 2 (2.5 mol%) with PhSiH 3 in C 6 D 6 at 1 bar of

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“…More specifically, in 2012 Baba and co-workers [86] reported the reduction of CO 2 with polymethylhydrosiloxane (PMHS) catalysed by a copper(I) complex formed in situ from Cu(OAc) 2 H 2 O and 1,2-bis(diphenylphosphino)-benzene (L17, Figure 8). In a subsequent report, Baba and co-workers followed the above methodology in the Hou and co-workers have reported a copper-based catalyst for the hydrosilylation of CO 2 with a hydrosilane as well [92].…”

Section: Hydrosilylation and Hydroboration Of Comentioning

confidence: 99%

Using sustainable metals to carry out “green” transformations: Fe- and Cu-catalyzed CO2 monetization

Pinaka

Vougioukalakis

2015

Coordination Chemistry Reviews

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Copper-Catalyzed Formic Acid Synthesis from CO₂ with Hydrosilanes and H₂O

Cited by 159 publications

References 37 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

Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion

Using sustainable metals to carry out “green” transformations: Fe- and Cu-catalyzed CO2 monetization

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Copper-Catalyzed Formic Acid Synthesis from CO2 with Hydrosilanes and H2O

Cited by 159 publications

References 37 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

Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion

Using sustainable metals to carry out “green” transformations: Fe- and Cu-catalyzed CO2 monetization

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Copper-Catalyzed Formic Acid Synthesis from CO₂ with Hydrosilanes and H₂O