Hydrogenation of CO<sub>2</sub> to Formate with H<sub>2</sub>: Transition Metal Free Catalyst Based on a Lewis Pair

Zhao, Tianxiang; Hu, Xingbang; Wu, Youting; Zhang, Zhibing

doi:10.1002/anie.201809634

Cited by 83 publications

(54 citation statements)

References 122 publications

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“…The B–O bond has a length of 1.522(3) Å. This is in analogy to the B–O distance of B(C 6 F 5 ) 3 adducts of formate (1.532 Å), or 2‐(pyridin‐2‐yl)phenol (1.520 Å) . The polyhedron BC 3 O is tetrahedral with bond angles C–B1–O1 and C–B1–C in the range of 103.1(2)–112.0(2)° and 106.3(2)–114.6(2)°, respectively.…”

Section: Resultsmentioning

confidence: 85%

Betaine–N‐Heterocyclic Carbene Interconversions of Quinazolin‐4‐One Imidazolium Mesomeric Betaines. Sulfur, Selenium, and Borane Adduct Formation

et al. 2020

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Reaction of N-alkylated imidazoles with 2-chloro-4quinazolinone gave mesomeric betaines, 2-(1-alkyl-1H-imidazolium-3-yl)quinazolin-4-olates, for which three tautomeric forms of N-heterocyclic carbenes (NHCs) can be formulated, in addition to an anionic NHC after deprotonation. The NHC tautomers were trapped with sulfur, selenium, triethylborane, and triphenylborane as thiones, selenones and borane adducts, respectively. We obtained two isomers of the cyclic borane adducts, diazaboroloquinazolinones with [1,5-a] and [5,1-b]-type fusion between the quinazolinone and the diazaborole rings.[a] Scheme 3. Synthesis of the target betaines; 15 N-labeled atoms are marked in blue. Numbering. The index "b" stands for "mesomeric betaine". Scheme 4. Betaine, NHC tautomers and anionic NHC of 13. 452 stants (J C-N3 ) and by 1D 15 N NMR spectra (see Table S1 and Fig. S2, Supporting Information). The long-range 1 H-15 N couplings (J HN ) with 15 N labeled and unlabeled nitrogen atoms (at natural 15 Eur.

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Section: Resultsmentioning

confidence: 85%

Betaine–N‐Heterocyclic Carbene Interconversions of Quinazolin‐4‐One Imidazolium Mesomeric Betaines. Sulfur, Selenium, and Borane Adduct Formation

et al. 2020

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“…By combining the copper catalyst and Lewis pair, hydrogenation of carbon dioxide into formate is realized (Romero et al, 2018). Latter, X. Hu and Y. Wu group reports the first catalytic hydrogenation process of CO 2 to formate using transition metal free catalyst (B(C 6 F 5 ) 3 /M 2 CO 3 , M = Na, K, and Cs) (Zhao et al, 2019). These results open new vistas in the field of FLPs facilitated CO 2 capture and hydrogenation.…”

Section: Frustrated Lewis Pairs (Flps)mentioning

confidence: 99%

CO2 Capture and in situ Catalytic Transformation

You

et al. 2019

Front. Chem.

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The escalating rate of fossil fuel combustion contributes to excessive CO 2 emission and the resulting global climate change has drawn considerable attention. Therefore, tremendous efforts have been devoted to mitigate the CO 2 accumulation in the atmosphere. Carbon capture and storage (CCS) strategy has been regarded as one of the promising options for controlling CO 2 build-up. However, desorption and compression of CO 2 need extra energy input. To circumvent this energy issue, carbon capture and utilization (CCU) strategy has been proposed whereby CO 2 can be captured and in situ activated simultaneously to participate in the subsequent conversion under mild conditions, offering valuable compounds. As an alternative to CCS, the CCU has attracted much concern. Although various absorbents have been developed for the CCU strategy, the direct, in situ chemical conversion of the captured CO 2 into valuable chemicals remains in its infancies compared with the gaseous CO 2 conversion. This review summarizes the recent progress on CO 2 capture and in situ catalytic transformation. The contents are introduced according to the absorbent types, in which different reaction type is involved and the transformation mechanism of the captured CO 2 and the role of the absorbent in the conversion are especially elucidated. We hope this review can shed light on the transformation of the captured CO 2 and arouse broad concern on the CCU strategy.

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“…In this regard, catalysts based on precious transition metals such as rhodium, ruthenium, and iridium, and base metal catalysts like iron, nickel, and cobalt have been extensively employed to activate CO 2 to form formic acid, formate, formaldehyde, methanol, methane, acetals, and carbon monoxide . Nevertheless, recently, there has been significant interest in the exploration of transition‐metal‐free catalysts for CO 2 activation, with several catalysts based on main‐group elements, such as frustrated Lewis pairs, N‐heterocyclic carbenes, and pincer‐type phosphorus compounds developed. Clearly, a sophisticated activation strategy is the key to the utilization of CO 2 in an efficient and economic manner.…”

Section: Introductionmentioning

confidence: 99%

Electride‐Sponsored Radical‐Controlled CO₂Reduction to Organic Acids: A Computational Design

Tang

Zhou

et al. 2020

Chemistry A European J

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Converting CO 2 into high-value chemicals has been regardeda sa nimportant solution for as ustainable low-carbon economy.I nt his work, we have theoretically designed an innovative strategy for the absorptiona nd activation of CO 2 by the electride N3Li, that is,1 ,3,5(2,6)-tripyridinacyclohexaphane (N3) intercalated by lithium.D FT computations showed that the interaction of CO 2 with N3Li leads to the catalytic complex N3Li(h 2 -O 2 C), which can initiate the radical-controlled reduction of anotherC O 2 to form organic acids through radical reactions in the gas phase. The CO 2 reductionc onsists of four steps:( 1) The formation of N3Li(h 2 -O 2 C) through the combinationo fN 3Li and CO 2 ,(2) hydrogen abstraction from RH (R = H, CH 3 ,a nd C 2 H 5 )b yN 3Li(h 2 -O 2 C) to form the radical RC and N3Li(h 2 -O 2 C)H, (3) the combination of CO 2 and the radicalRC to form RCOOC,and (4) intermolecular hydrogen transferf rom the intermediateN 3Li(h 2 -O 2 C)H to RCOOC.I nt he whole reactionp rocess, the CO 2 moiety in the complex N3Li(h 2 -O 2 C) maintains ac ertainr adical character at the carbon atom of CO 2 and plays as elf-catalyzing role. This work represents the first example of electridesponsored radical-controlledC O 2 reduction,a nd thus provides an alternative strategy for CO 2 conversion.

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Hydrogenation of CO₂ to Formate with H₂: Transition Metal Free Catalyst Based on a Lewis Pair

Cited by 83 publications

References 122 publications

Betaine–N‐Heterocyclic Carbene Interconversions of Quinazolin‐4‐One Imidazolium Mesomeric Betaines. Sulfur, Selenium, and Borane Adduct Formation

Betaine–N‐Heterocyclic Carbene Interconversions of Quinazolin‐4‐One Imidazolium Mesomeric Betaines. Sulfur, Selenium, and Borane Adduct Formation

CO2 Capture and in situ Catalytic Transformation

Electride‐Sponsored Radical‐Controlled CO₂Reduction to Organic Acids: A Computational Design

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Hydrogenation of CO2 to Formate with H2: Transition Metal Free Catalyst Based on a Lewis Pair

Cited by 83 publications

References 122 publications

Betaine–N‐Heterocyclic Carbene Interconversions of Quinazolin‐4‐One Imidazolium Mesomeric Betaines. Sulfur, Selenium, and Borane Adduct Formation

Betaine–N‐Heterocyclic Carbene Interconversions of Quinazolin‐4‐One Imidazolium Mesomeric Betaines. Sulfur, Selenium, and Borane Adduct Formation

CO2 Capture and in situ Catalytic Transformation

Electride‐Sponsored Radical‐Controlled CO2Reduction to Organic Acids: A Computational Design

Contact Info

Product

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Hydrogenation of CO₂ to Formate with H₂: Transition Metal Free Catalyst Based on a Lewis Pair

Electride‐Sponsored Radical‐Controlled CO₂Reduction to Organic Acids: A Computational Design