Homogeneous catalytic reduction of CO<sub>2</sub> with hydrosilanes

Fernández-Álvarez, Francisco J.; Aitani, Abdullah M.; Oro, Luis A.

doi:10.1039/c3cy00948c

Cited by 195 publications

(124 citation statements)

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“…The reduction of CO 2 with hydrosilanes has been recently reviewed [24]. This section will concentrate on the hydrosilylation reactions catalyzed by boranes.…”

Section: Catalytic Reduction Of Co 2 By Boraneactivated Hydrosilanesmentioning

confidence: 99%

“…At the fundamental level, a more efficient and controlled activation of CO 2 would allow one to i) decrease the level of energy input and / or ii) increase the molecular complexity of the product and as a consequence the added-value of the compounds synthesized from CO 2 . The last decade witnessed intense interests in the homogeneous reduction of CO 2 with dihydrogen [20][21][22][23], hydrosilane [24] and hydroborane as reducing agents. While CO 2 hydrogenation appears as the ideal reaction in term of atom economy, a sustainable source of "carbon free" dihydrogen and milder reaction conditions remain to be described.…”

Section: Introductionmentioning

confidence: 99%

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Boron-mediated activation of carbon dioxide

Bontemps

2016

Coordination Chemistry Reviews

191

109

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“…The reduction of CO 2 with hydrosilanes has been recently reviewed [24]. This section will concentrate on the hydrosilylation reactions catalyzed by boranes.…”

Section: Catalytic Reduction Of Co 2 By Boraneactivated Hydrosilanesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Boron-mediated activation of carbon dioxide

Bontemps

2016

Coordination Chemistry Reviews

191

109

View full text Add to dashboard Cite

“…In this regard, the catalytic reduction of CO 2 with hydrosilanes has emerged as an useful methodology for the transformation of CO 2 into value‐added chemicals under mild reaction conditions . Conversely, CO 2 ‐hydrosilylation processes are commonly unselective and afford mixtures of reduction products . Therefore, the development of active and selective catalytic systems for the reduction of CO 2 with silanes is of great interest.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights on the Reduction of CO₂ to Silylformates Catalyzed by Ir‐NSiN Species

Julián

Guzmán

Jaseer

et al. 2017

Chemistry A European J

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The hydrosilylation of CO with different silanes such as HSiEt , HSiMe Ph, HSiMePh , HSiMe(OSiMe ) , and HSi(OSiMe ) in the presence of catalytic ammounts of the iridium(III) complex [Ir(H)(CF CO )(NSiN*)(coe)] (1; NSiN*=fac-bis-(4-methylpyridine-2-yloxy); coe=cis-cyclooctene) has been comparatively studied. The activity of the hydrosilylation catalytic system based on 1 depends on the nature of the reducing agent, where HSiMe(OSiMe ) has proven to be the most active. The aforementioned reactions were found to be highly selective toward the formation of the corresponding silylformate. It has been found that using 1 as catalyst precursor above 328 K decreases the activity through a thermally competitive mechanistic pathway. Indeed, the reduction of the ancillary trifluoroacetate ligand to give the corresponding silylether CF CH OSiR has been observed. Moreover, mechanistic studies for the 1-catalyzed CO -hydrosilylation reaction based on experimental and theoretical studies suggest that 1 prefers an inner-sphere mechanism for the CO reduction, whereas the closely related [Ir(H)(CF SO )(NSiN)(coe)] catalyst, bearing a triflate instead of trifluoroacetate ligand, follows an outer-sphere mechanism.

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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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Homogeneous catalytic reduction of CO₂ with hydrosilanes

Abstract: Catalytic CO2 hydrosilylation is a chemical process that could be potentially applied to large-scale transformations.

Cited by 195 publications

References 71 publications

Boron-mediated activation of carbon dioxide

Boron-mediated activation of carbon dioxide

Mechanistic Insights on the Reduction of CO₂ to Silylformates Catalyzed by Ir‐NSiN Species

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

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Homogeneous catalytic reduction of CO2 with hydrosilanes

Abstract: Catalytic CO2 hydrosilylation is a chemical process that could be potentially applied to large-scale transformations.

Cited by 195 publications

References 71 publications

Boron-mediated activation of carbon dioxide

Boron-mediated activation of carbon dioxide

Mechanistic Insights on the Reduction of CO2 to Silylformates Catalyzed by Ir‐NSiN Species

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

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Homogeneous catalytic reduction of CO₂ with hydrosilanes

Mechanistic Insights on the Reduction of CO₂ to Silylformates Catalyzed by Ir‐NSiN Species