Highly efficient catalytic hydrosilylation of carbon dioxide by an N-heterocyclic carbene copper catalyst

Zhang, Liang; Cheng, Jianhua; Hou, Zhaomin

doi:10.1039/c3cc41838c

Cited by 148 publications

(105 citation statements)

References 36 publications

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“…A plausible mechanism was proposed involving the formation of a hydride species. The CO 2 insertion promotes the formation of a copper formate complex, which by reaction with the silane releases the hydrosilylated product [105]. [108].…”

Section: Carboxylation Of Boronic Estersmentioning

confidence: 99%

Copper–NHC complexes in catalysis

Lazreg

Nahra

Cazin

2015

Coordination Chemistry Reviews

225

109

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Section: Carboxylation Of Boronic Estersmentioning

confidence: 99%

Copper–NHC complexes in catalysis

Lazreg

Nahra

Cazin

2015

Coordination Chemistry Reviews

225

109

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“…S21 †). The variation of solvent relates to an increase in turnover frequencies (TOFs), determined from the time taken to consume the hydrosilane at 80°C, of 3.3 h −1 for C 6 D 6 to 40 h −1 for d 7 -DMF. The increase in rate is, in part, due to the increased solubility of CO 2 in the more polar solvent; indeed, a reaction carried out in CD 3 CN under 2 bar of CO 2 shows complete hydrosilane depletion within 1.5 h (Fig.…”

Section: Reduction Of Carbon Dioxidementioning

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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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14] In contrast, only a handful of examples of silver-catalyzed hydrogenation and hydrosilylation are known. [15][16][17][18][19][20] For example, AgOTf has been shown to catalyze the hydrosilylation of aryl aldehydes in the presence of Me 2 PhSiH and PEt 3 .…”

mentioning

confidence: 99%

Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag₆H₄(dppm)₄(OAc)₂] and [Cu₃H(dppm)₃(OAc)₂]

2016

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ABSTRACT:The group 11 hydride clusters [Ag 6 H 4 (dppm) 4 (OAc) 2 ](1) and(2) (dppm = 1,1-bis(diphenylphosphino)methane) were synthesized in moderate yields from the reaction of M(OAc) (M = Ag, Cu) with Ph 2 SiH 2 , in the presence of dppm. Complex 1 is the first structurally characterized homometallic polyhydrido silver cluster to be isolated. Both 1 and 2 catalyze the hydrosilylation of (,-unsaturated) ketones. Notably, this represents the first example of hydrosilylation with an authentic silver hydride complex.

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Highly efficient catalytic hydrosilylation of carbon dioxide by an N-heterocyclic carbene copper catalyst

Cited by 148 publications

References 36 publications

Copper–NHC complexes in catalysis

Copper–NHC complexes in catalysis

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

Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag₆H₄(dppm)₄(OAc)₂] and [Cu₃H(dppm)₃(OAc)₂]

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Highly efficient catalytic hydrosilylation of carbon dioxide by an N-heterocyclic carbene copper catalyst

Cited by 148 publications

References 36 publications

Copper–NHC complexes in catalysis

Copper–NHC complexes in catalysis

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

Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag6H4(dppm)4(OAc)2] and [Cu3H(dppm)3(OAc)2]

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Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag₆H₄(dppm)₄(OAc)₂] and [Cu₃H(dppm)₃(OAc)₂]