Reactions of carbon dioxide with transition metal compounds

Vol'pin, M. E.; Kolomnikov, I. S.

doi:10.1351/pac197333040567

Cited by 74 publications

(18 citation statements)

References 33 publications

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“…For the foreseeable future, large amounts of CO 2 are available as potential feedstocks from various industrial processes in high concentration [14] . Even in long‐term scenarios, if full decarbonization of all non‐chemical sectors would be achieved, the carbon reserves in the various forms of CO 2 (e.g., in the atmosphere, hydrosphere, and carbonates in the terrestrial environment) considerably exceed those of fossil resources [15] . Consequently, the conversion of carbon dioxide into fuels, basic and fine chemicals, as well as polymer materials offers tremendous potential to utilize carbon‐free electricity from increasingly deployed renewable energy technologies in chemical added‐value chains [16] .…”

Section: Background and Motivationmentioning

confidence: 99%

“…Since the 1970s, many scientific breakthroughs and developments have proved that catalytically active transition metal catalysts can convert CO 2 into more valuable chemicals via thermochemical routes [15, 29] . While industrial implementation is already pursued in individual cases, [30] the broad application of this strategy still faces significant challenges.…”

Section: Background and Motivationmentioning

confidence: 99%

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Transition Metal Complexes as Catalysts for the Electroconversion of CO₂: An Organometallic Perspective

2021

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The electrocatalytic transformation of carbon dioxide has been a topic of interest in the field of CO2 utilization for a long time. Recently, the area has seen increasing dynamics as an alternative strategy to catalytic hydrogenation for CO2 reduction. While many studies focus on the direct electron transfer to the CO2 molecule at the electrode material, molecular transition metal complexes in solution offer the possibility to act as catalysts for the electron transfer. C1 compounds such as carbon monoxide, formate, and methanol are often targeted as the main products, but more elaborate transformations are also possible within the coordination sphere of the metal center. This perspective article will cover selected examples to illustrate and categorize the currently favored mechanisms for the electrochemically induced transformation of CO2 promoted by homogeneous transition metal complexes. The insights will be corroborated with the concepts and elementary steps of organometallic catalysis to derive potential strategies to broaden the molecular diversity of possible products.

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Section: Background and Motivationmentioning

confidence: 99%

Section: Background and Motivationmentioning

confidence: 99%

Transition Metal Complexes as Catalysts for the Electroconversion of CO₂: An Organometallic Perspective

2021

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“…In dem Komplex [Co(pr-salen) (CO,)K(THF)], (2) ist das CO, iiber eine Lewis-SaurelBase-Wechselwirkung zwischen dem Kohlenstoffatom des C 0 2 und dem Co(1)-Ion koordinied, wobei eine Wechselwirkung zwischen den Sauerstoffatomen des CO, und den K+-Ionen zu einer zusatzlichen Stabilisierung fiihrt. Bis jetzt sind (1) …”

Section: Physikalische Hinweise Auf C02-koordination Und -Aktivierungunclassified

Die CO₂–Aktivierung durch Metallkomplexe

Braunstein¹

1981

Nachr. Chem. Tech. Lab.

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“…However, its inherent thermodynamic stability and kinetic inertness poses significant challenges so as to achieve CO 2 activation and functionalisation. The formation of coordination bonds with inert molecules is one of the most powerful and popular ways for inducing (fixing) them for subsequent reaction [18].…”

Section: Introductionmentioning

confidence: 99%

“…A variety of transition metal complexes with M-OR fragments undergo insertion reactions with CO 2 [4,6,7,18]. If R is an alkyl or aryl group, corresponding alkyl or aryl carbonate species are formed, while if R is a H atom, bicarbonate species are formed.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of Atmospheric CO₂ Fixation in the Cavities of a Dinuclear Cryptate

2012

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Using density functional theory (DFT) methods, we have investigated two possible mechanisms for atmospheric CO 2 fixation in the cavity of the dinuclear zinc (II) octaazacryptate, and the subsequent reaction with methanol whereby this latter reaction transforms the (essentially) chemically inert CO 2 into useful products. The first mechanism (I) was proposed by Chen et al. [Chem. Asian J. 2007, 2, 710], and involves the attachment of one CO 2 molecule onto the hydroxyl-cryptate form, resulting in the formation of a bicarbonate-cryptate species and subsequent reaction with one methanol molecule. In addition, we suggest another mechanism that is initiated via the attachment of a methanol molecule onto one of the Zn-centres, yielding a methoxy-cryptate species. The product is used to activate a CO 2 molecule and generate a methoxycarbonate-cryptate. The energy profiles of both mechanisms were determined and we conclude that, while both mechanisms are energetically feasible, free energy profiles suggest that the scheme proposed by Chen et al. is most likely.

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Reactions of carbon dioxide with transition metal compounds

Cited by 74 publications

References 33 publications

Transition Metal Complexes as Catalysts for the Electroconversion of CO₂: An Organometallic Perspective

Transition Metal Complexes as Catalysts for the Electroconversion of CO₂: An Organometallic Perspective

Die CO₂–Aktivierung durch Metallkomplexe

Mechanism of Atmospheric CO₂ Fixation in the Cavities of a Dinuclear Cryptate

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Reactions of carbon dioxide with transition metal compounds

Cited by 74 publications

References 33 publications

Transition Metal Complexes as Catalysts for the Electroconversion of CO2: An Organometallic Perspective

Transition Metal Complexes as Catalysts for the Electroconversion of CO2: An Organometallic Perspective

Die CO2–Aktivierung durch Metallkomplexe

Mechanism of Atmospheric CO2 Fixation in the Cavities of a Dinuclear Cryptate

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Product

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Transition Metal Complexes as Catalysts for the Electroconversion of CO₂: An Organometallic Perspective

Transition Metal Complexes as Catalysts for the Electroconversion of CO₂: An Organometallic Perspective

Die CO₂–Aktivierung durch Metallkomplexe

Mechanism of Atmospheric CO₂ Fixation in the Cavities of a Dinuclear Cryptate