Carbon Monoxide as a Chemical Feedstock: Carbonylation Catalysis

Leeuwen, Piet W. N. M. van; Freixa, Zoraida

doi:10.1002/9783527609352.ch9

Cited by 11 publications

(12 citation statements)

References 71 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…If the overall reactioni se ndothermic, these thermochemical processes can also be an energy storage technology to convert waste or renewable thermal energy into useful chemical bonds. [13,14] Thermochemical (redox) cycles have been studied to reduce CO 2 using oxygen carriers such as CeO 2 , [15] Zn/ZnO [16] and doped LaMnO 3 . [17] These cycles usually operates at different oxidation and reduction temperatures.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen‐assisted Carbon Dioxide Thermochemical Reduction on La_0.9Ca_0.1FeO_3−δ Membranes: A Kinetics Study

Ghoniem

2018

ChemSusChem

View full text Add to dashboard Cite

show abstract

Section: Introductionmentioning

confidence: 99%

Hydrogen‐assisted Carbon Dioxide Thermochemical Reduction on La_0.9Ca_0.1FeO_3−δ Membranes: A Kinetics Study

Ghoniem

2018

ChemSusChem

View full text Add to dashboard Cite

show abstract

“…This reaction is particularly interesting because catalytic versions could be used to convert CO 2 into CO, a well-utilized carbon feedstock. 44 This could serve as an alternative to fossil fuel-sourced CO (via syngas). 45 Thus, many CO 2 reduction reactions of these types are known for metals that are sufficiently reducing.…”

Section: −mentioning

confidence: 99%

“…The reverse of step a is also possible: the reduction of a CO 2 complex back to a CO complex. This reaction is particularly interesting because catalytic versions could be used to convert CO 2 into CO, a well-utilized carbon feedstock . This could serve as an alternative to fossil fuel-sourced CO (via syngas) .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Molybdenum Dihapto Carbon Dioxide Complexes via Oxidation of a Carbonyl Ligand

et al. 2021

View full text Add to dashboard Cite

A carbonyl ligand can be thermally liberated from TpRMo(NO)(CO)2 in the presence of a potential σ-donor ligand (L) to give TpRMo(NO)(L)(CO), where TpR = hydridotris(pyrazolyl)borate (Tp) or hydridotris(3,5-dimethylpyrazolyl)borate (Tp*). For Tp, complexes featuring L = 1-methylimidazole (1-MeIm), 4-(dimethylamino)pyridine (4-DMAP), PMe3, PMe2Ph, PPh3, and P(OMe)3 have been prepared. In addition, an N-heterocyclic-carbene complex, where L = 1,3-dimethylimidazol-2-ylidene (NHC), has also been prepared using 1,3-dimethylimidazolium-2-carboxylate as the carbene-transfer agent. For Tp*, complexes featuring L = 1-MeIm, 4-DMAP, PMe3, pyridine, and P(OMe)3 have been prepared. Oxidation of the more electron-rich TpRMo(NO)(L)(CO) complexes using a hydroperoxide gives η2-CO2 complexes, TpRMo(NO)(L)(η2-CO2). For Tp, η2-CO2 complexes where L = 1-MeIm, NHC, PMe3, and PMe2Ph have been isolated. For Tp*, η2-CO2 complexes where L = 1-MeIm and PMe3 have been isolated. Carbonyl stretching frequencies indicate the susceptibility of TpRMo(NO)(L)(CO) complexes to oxidation to form an η2-CO2 complex. Carbonyl complexes featuring νCO values of >1885 cm–1 did not result in observable η2-CO2 complexes upon oxidation. The η2-CO2 complexes are most often formed as mixtures of two coordination diastereomers that can interconvert in solution. For the PMe3 complexes, a single diastereomer in which the uncoordinated oxygen of the CO2 ligand points toward PMe3 is heavily favored at equilibrium (>30:1). These PMe3 η2-CO2 complexes have also been analyzed by X-ray diffraction. The η2-CO2 complexes are air stable and thermally stable at room temperature in solution. Reduction of TpRMo(NO)(L)(η2-CO2) back to TpRMo(NO)(L)(CO) can be accomplished using chemical reductants, including LiBH4, LiAlH4, and a mixture of magnesium powder and P(NMe2)3.

show abstract

“…The reduction of carbon dioxide to carbon monoxide is one of the important transformations of CO 2 and presents an opportunity to utilize carbon dioxide on an industrial scale. CO is used as a feedstock in a range of industrial processes including the synthesis of methanol and acetic acid . Currently, carbon monoxide is industrially produced through the reforming of methane , or through coal gasification processes , as syngas (a mixture of CO and H 2 ), which may be further purified or used directly as a chemical feedstock.…”

Section: Introductionmentioning

confidence: 99%

Fe(0)-Mediated Reductive Disproportionation of CO₂

Jurd

Bhadbhade

et al. 2020

Organometallics

View full text Add to dashboard Cite

The zero-valent iron phosphine [Fe(N 2 )(dmpe) 2 ] (2) reacts with CO 2 to form the(3) through the reductive coupling of two molecules of carbon dioxide. The formation of metalacycle 3 proceeds through a stepwise reaction with carbon dioxide to form, initially, the isolable 1), which reacts with a second molecule of CO 2 to form the 5-membered metalacycle. This sequence represents the first experimental evidence for the formation of a κ 2 C,O-FeC 2 O 4 metalacycle via an η 2 (C,O)-CO 2 precursor. Isotopic labeling was used to demonstrate that the initial coordinated CO 2 molecule forms the metal-bound carbonyl moiety in the metalacycle, while the second molecule of CO 2 forms the carbonyl β to the iron center. The metalo-2,4-dioxolane-3,5-dione cis-[Fe(C(O)OC(O)O-κ 2 C,O)(dmpe) 2 ] (3) breaks down with loss of CO to yield the iron carbonate cis-[Fe(CO 3 -κ 2 O,O)(dmpe) 2 ] (5). In the presence of a CO scavenger such as [Fe(N 2 )(dmpe) 2 ], CO is trapped to give [Fe(CO)(dmpe) 2 ] (4). This is the first direct experimental evidence for a κ 2 C,O-C 2 O 4 metalacycle being a key intermediate in the reductive disproportionation of CO 2 to CO and CO 3 2− .

show abstract

Carbon Monoxide as a Chemical Feedstock: Carbonylation Catalysis

Cited by 11 publications

References 71 publications

Hydrogen‐assisted Carbon Dioxide Thermochemical Reduction on La_0.9Ca_0.1FeO_3−δ Membranes: A Kinetics Study

Hydrogen‐assisted Carbon Dioxide Thermochemical Reduction on La_0.9Ca_0.1FeO_3−δ Membranes: A Kinetics Study

Synthesis of Molybdenum Dihapto Carbon Dioxide Complexes via Oxidation of a Carbonyl Ligand

Fe(0)-Mediated Reductive Disproportionation of CO₂

Contact Info

Product

Resources

About

Carbon Monoxide as a Chemical Feedstock: Carbonylation Catalysis

Cited by 11 publications

References 71 publications

Hydrogen‐assisted Carbon Dioxide Thermochemical Reduction on La0.9Ca0.1FeO3−δ Membranes: A Kinetics Study

Hydrogen‐assisted Carbon Dioxide Thermochemical Reduction on La0.9Ca0.1FeO3−δ Membranes: A Kinetics Study

Synthesis of Molybdenum Dihapto Carbon Dioxide Complexes via Oxidation of a Carbonyl Ligand

Fe(0)-Mediated Reductive Disproportionation of CO2

Contact Info

Product

Resources

About

Hydrogen‐assisted Carbon Dioxide Thermochemical Reduction on La_0.9Ca_0.1FeO_3−δ Membranes: A Kinetics Study

Hydrogen‐assisted Carbon Dioxide Thermochemical Reduction on La_0.9Ca_0.1FeO_3−δ Membranes: A Kinetics Study

Fe(0)-Mediated Reductive Disproportionation of CO₂