A Highly Active Phosphine–Borane Organocatalyst for the Reduction of CO<sub>2</sub> to Methanol Using Hydroboranes

Courtemanche, Marc-André; Légaré, Marc‐André; Maron, Laurent; Fontaine, Frédéric‐Georges

doi:10.1021/ja404585p

Cited by 311 publications

(181 citation statements)

References 39 publications

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“…The preparation of 1-cathecolboryl-2-diphenylphosphinobenzene was reported and these kinds of FLP compounds catalyse the hydroboration of CO 2 in the presence of catecholborane to afford cat-BOB-cat and MeOB-cat (as depicted in Scheme 19), and the latter could be hydrolysed to methanol. 96 The reaction was performed under mild conditions (p(CO 2 ) = 1 bar, T max = 70 ºC) observing a maximum TOF of 973 h -1 (TONs up to 2950 using BH 3 ·SMe 2 as hydrogen source) reaching similar rates to the ones reported for transition-metal based catalysts.…”

Section: 137-139mentioning

confidence: 54%

“…95 Their mechanism of action, as illustrated in Scheme 6 for aryl-bridged phosphine-borane FLPs, involves CO 2 binding and formation of a zwitterionic carboxylated FLP adduct. 96 Depending on the reaction partner, FLPs can be catalytically active towards CO 2 coupling to epoxides 97 or, in presence of an appropriate reducing agent, i.e. trialkylsilanes, towards its reduction.…”

Section: 92-94mentioning

confidence: 99%

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Sustainable conversion of carbon dioxide: the advent of organocatalysis

2015

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The conversion of carbon dioxide (CO 2 ), an abundant renewable carbon reagent, into chemicals of academic and industrial interest is of imminent importance to create a higher degree of sustainability in chemical processing and production. Recent progress in this field is characterised by a plethora of organic molecules able to mediate the conversion of suitable substrates in the presence of CO 2 into a variety of value-added commodities with advantageous features combining cost-effectiveness, metalfree transformations and general substrate activation profiles. In this review, the latest developments are discussed in the field of CO 2 catalysis with a focus on organo-mediated conversions and their increasing importance as to serve as practicable alternatives for metal-based processes. Also a critical assessment of the state-of-the-art is presented with attention on those features that need further attention to lift the usefulness of organocatalysis in the production of organic molecules of potential commercial interest.

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Section: 137-139mentioning

confidence: 54%

Section: 92-94mentioning

confidence: 99%

Sustainable conversion of carbon dioxide: the advent of organocatalysis

2015

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“…It was also found that the hydrogen rich BH3.SMe2 could be used as a reducing agent with record-breaking TOF values of 853 h -1 at 70 °C (Scheme 8) [37].…”

Section: Ambiphilic Molecules As Catalysts For the Reduction Of Carbomentioning

confidence: 98%

“…Although the reduction of CO2 has been shown to be possible in some instances [22,[35][36], no FLP system was able to perform efficient and selective catalytic transformations until our original report that demonstrated the catalytic activity of 1-Ph2P-2-Bcat-C6H4 (7, cat = catechol) for the hydroboration of CO2 to methoxyboranes, species that can be readily hydrolysed to methanol [37].…”

Section: Ambiphilic Molecules As Catalysts For the Reduction Of Carbomentioning

confidence: 99%

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

Fontaine

Courtemanche

Légaré

et al. 2017

Coordination Chemistry Reviews

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102

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This is the peer reviewed version of the following article: [Design Principles in Frustrated Lewis KeywordsFrustrated Lewis pairs, Ambiphilic molecules, Boron, Aluminum, Carbon dioxide, Methanol, C-H activation. Highlights 1.Phosphine-aluminum frustrated Lewis pairs (FLPs) can activate CO2 but show significant stability issues. 2.The Lewis acidity and basicity need to be fine-tuned to the desired reactivity for efficient FLP catalysis.3. FLP catalysts need to generate strong hydrides to reduce catalytically carbon dioxide. 4.Transition metal catalysis can serve as an inspiration for the design of metal-free catalysts for many transformations, including the borylation of heteroarenes. Graphical abstract AbstractThis account describes our work on the use of ambiphilic molecules as catalysts for the reduction of carbon dioxide. Starting with the discovery that aluminum ambiphilic species (Me2PCH2AlMe2)2 (1) and Al(C6H4-PPh3)3 (5) could coordinate CO2 but showed significant instability, we found that phosphinoborane Ph2P-2-Bcat-C6H4 (7) was an exceptional catalyst for the hydroboration of CO2 to methoxyboranes, a molecule that can be readily hydrolyzed to methanol. A mechanistic investigation allowed us to outline the similarities between the catalytic activity of frustrated Lewis pairs (FLPs) and that of transition metal complexes. We were able to extrapolate four important guidelines, described in this account, to synthesize efficient metal-free catalysts. We demonstrate that using these concepts it was possible to rationally design FLP catalysts for the C-H borylation of heteroarenes.

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“…Hazari and co-workers [16] reported the allene carboxylation with CO 2 using a PSiP pincer ligand supported palladium complex as the catalyst in the hydroboration of CO 2 . Maron and co-workers [17,18] reported the phosphine-borane-mediated hydroboration of CO 2 to methanol using an organocatalyst 1-Bcat-2-PPh 2 -C 6 H 4 (Bcat = catecholboryl). Their mechanistic study showed that the simultaneous activation of both the reducing agent and CO 2 plays an important role in the catalytic reaction.…”

Section: Introductionmentioning

confidence: 99%

Reaction Mechanisms of CO2 Reduction to Formaldehyde Catalyzed by Hourglass Ru, Fe, and Os Complexes: A Density Functional Theory Study

Dong

Yang

et al. 2016

Catalysts

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(1 Os ), were studied computationally by using the density functional theory (DFT). 1 Ru is a recently reported highly efficient catalyst for this reaction. 1 Fe and 1 Os are two analogues of 1 Ru with the Ru atom replaced by Fe and Os, respectively. The total free energy barriers of the reactions catalyzed by 1 Ru , 1 Fe and 1 Os are 24.2, 24.0 and 29.0 kcal/mol, respectively. With a barrier close to the experimentally observed Ru complex, the newly proposed iron complex is a potential low-cost catalyst for the reduction of carbon dioxide to formaldehyde under mild conditions. The electronic structures of intermediates and transition states in these reactions were analyzed by using the natural bond orbital theory.

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A Highly Active Phosphine–Borane Organocatalyst for the Reduction of CO₂ to Methanol Using Hydroboranes

Cited by 311 publications

References 39 publications

Sustainable conversion of carbon dioxide: the advent of organocatalysis

Sustainable conversion of carbon dioxide: the advent of organocatalysis

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

Reaction Mechanisms of CO2 Reduction to Formaldehyde Catalyzed by Hourglass Ru, Fe, and Os Complexes: A Density Functional Theory Study

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A Highly Active Phosphine–Borane Organocatalyst for the Reduction of CO2 to Methanol Using Hydroboranes

Cited by 311 publications

References 39 publications

Sustainable conversion of carbon dioxide: the advent of organocatalysis

Sustainable conversion of carbon dioxide: the advent of organocatalysis

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

Reaction Mechanisms of CO2 Reduction to Formaldehyde Catalyzed by Hourglass Ru, Fe, and Os Complexes: A Density Functional Theory Study

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A Highly Active Phosphine–Borane Organocatalyst for the Reduction of CO₂ to Methanol Using Hydroboranes