Production of Acrylic Acid through Nickel-Mediated Coupling of Ethylene and Carbon Dioxide—A DFT Study

Ohnishi Y., Nakao Y., Sato H., Sakaki S.

Oxidative addition of H2 to Ni(PH3)2 was theoretically studied as a prototype of nickel-catalyzed sigma-bond activation reaction, where CASSCF, CASPT2, CCSD(T), broken symmetry (Bs) MP2 to MP4(SDTQ), and DFT methods were employed. The CASPT2 method yields a reliable potential energy curve (PEC) when the active space consists of 10 electrons and 10 orbitals including five outer 3d' orbitals. The CCSD(T) method presents almost the same PEC as the CASPT2-calculated one, when either the ANO or the cc-pVTZ basis set is used for Ni. Bs-MP4(SDTQ)-calculated PEC is similar to those calculated by the CASPT2/ANO method, while the PEC is not smooth around the transition state. In the DFT calculation, ANO, cc-pVTZ, and triple-zeta quality basis sets (SDB) with Stuttgart-Dresden-Bonn effective core potentials (ECPs) must be used for Ni. The DFT-calculated reaction energy is somewhat smaller than the CASPT2- and CCSD(T)-calculated values, while B3PW91 and mPW1PW91 present moderately better energy changes than BLYP, B1LYP, and B3LYP. Oxidative addition of MeCN to Ni(PH3)2 was investigated by the DFT(B3PW91) and CCSD(T) methods. Almost the same activation barrier was calculated by these methods, when cc-pVTZ was employed for Ni. However, the DFT method moderately underestimates the binding energy of the reactant complex and the reaction energy compared to the CCSD(T) method. This oxidative addition exhibits interesting characteristic features, as follows: The barrier height relative to infinite separation is lower, and the product is more stable than those of the oxidative addition of C2H6. These differences are discussed in detail in terms of Ni-Me and Ni-CN bond energies and the participation of the CN pi* orbital to stabilization interaction in the transition state.

Fischer R., Langer J., Malassa A., Walther D., Görls H., Vaughan G.

The reaction of a nickelalactone with dppm, resulting in the formation of a stable binuclear Ni(I) complex with an acrylate, a Ph2P- and a dppm bridge, models a key step in the formation of acrylic acid from CO2 and ethylene.

Burlakov V.V., Arndt P., Baumann W., Spannenberg A., Rosenthal U.

The well-known zirconafuranone, obtained by the reaction of the decamethylzirconocene bis(trimethylsilyl)acetylene complex Cp*2Zr(η2-Me3SiC2SiMe3) with carbon dioxide, rearranges upon thermolysis to a complex with the [C5Me4−CH2−CH(Me3Si)C(CO)]2- ligand resulting from an electrophilic substitution of a hydrogen atom at one of the methyl groups of a Cp* ligand, a cleavage of the CO bond in the starting zirconafuranone, and a movement of the Me3Si groups from β-carbon to oxygen. Another example of the functionalization of a pentamethylcyclopentadienyl ligand by carbon dioxide was found with a complex obtained by the reaction of Cp*2ZrCl2 with magnesium in the presence of the butadiyne t-BuC⋮CC⋮Ct-Bu. This complex reacts by formally inserting 1 equiv of carbon dioxide into each of two ZrC bonds, but yields a dinuclear complex with twofold functionalized Cp* ligands acting as bridging dicarboxylato ligands, [O2C−CH2−C5Me3−CH2−CH(t-Bu)C(CCH-t-Bu)−CO2]3-. Both complexes result from a simple method of functional...

Louie J.

Shimizu K., Takimoto M., Sato Y., Mori M.

[Reaction: see text] Syntheses of alpha-silyl-beta,beta'-dialkyl alpha,beta-unsaturated carboxylic acids were achieved from silylated alkyne, carbon dioxide, and a zinc reagent using a catalytic amount of nickel complex in the presence of an excess amount of DBU. The regioselectivity of the introduction of CO2 into disubstituted alkyne is dependent on the electronic property of the substituent R on the alkyne because the thermodynamic stability of oxanickelacycle IV or V should be affected by conjugation of the substituent R with the carboxyl group in IV or V.

Jessop P.G., Joó F., Tai C.

Homogeneous hydrogenation of carbon dioxide continues to attract interest in the hope of finding active and selective catalysts for the production of valuable organics based on this cheap and abundant carbon source. This review covers advances published or in press since 1995. The survey of the field shows that while very active catalysts and co-catalysts have been discovered in this period for the production of formic acid and its derivatives, there has been only preliminary development of homogeneous catalysts for the production of other oxygenates (e.g. methanol, CO) and C n -compounds ( n > 1).

Pápai I., Schubert G., Mayer I., Besenyei G., Aresta M.

The mechanism of the experimentally observed formation of the five-membered nickela−carboxylate complex in the nickel(0)-assisted oxidative coupling of CO2 and C2H4 is revealed by means of density functional calculations. The reliability of the applied DFT methodology has been first assessed by comparison to high-level coupled-cluster calculations on a relevant model reaction. The most important stationary points on the potential energy surface associated with the title reaction have been located, and low-energy reaction pathways have been identified. We show that the C−C bond formation occurs in a single step by the reaction of a nickel−ethylene complex with an incoming CO2 molecule. The solvent effect and the influence of the ancillary ligands on the reaction energetics are examined, and both are shown to be important in these reactions.

Thomas C.D., Cameron A., Green R.E., Bakkenes M., Beaumont L.J., Collingham Y.C., Erasmus B.F., de Siqueira M.F., Grainger A., Hannah L., Hughes L., Huntley B., van Jaarsveld A.S., Midgley G.F., Miles L., et. al.

Climate change over the past ∼30 years has produced numerous shifts in the distributions and abundances of species1,2 and has been implicated in one species-level extinction3. Using projections of species' distributions for future climate scenarios, we assess extinction risks for sample regions that cover some 20% of the Earth's terrestrial surface. Exploring three approaches in which the estimated probability of extinction shows a power-law relationship with geographical range size, we predict, on the basis of mid-range climate-warming scenarios for 2050, that 15–37% of species in our sample of regions and taxa will be ‘committed to extinction’. When the average of the three methods and two dispersal scenarios is taken, minimal climate-warming scenarios produce lower projections of species committed to extinction (∼18%) than mid-range (∼24%) and maximum-change (∼35%) scenarios. These estimates show the importance of rapid implementation of technologies to decrease greenhouse gas emissions and strategies for carbon sequestration.

Schubert G., Pápai I.

The reaction path for the formation of a binuclear hydrido-acrylate complex in a CO(2)-C(2)H(4) coupling process is explored in detail by locating the key intermediates and transition states on model potential energy surfaces derived from density functional calculations on realistic models. The formation of the new C-C bond is shown to take place via oxidative coupling of coordinated CO(2) and C(2)H(4) ligands resulting in a metalla-lactone intermediate, which can rearrange to an agostic species allowing for a beta-hydrogen shift process. The overall reaction is predicted to be clearly exothermic with all intermediates lying below the reactants in energy, and the highest barrier steps correspond to C-C coupling and beta-hydrogen transfer. The phosphine ligands are found to play an important role in various phases of the reaction as their dissociation controls the coordination of CO(2), the formation of the agostic intermediate, and the dimerization process; furthermore, their presence facilitates the oxidative coupling by supplying electrons to the metal center. Our results provide a theoretical support for the reaction mechanism proposed from experimental observations. The effect of the solvent medium on the relative energy of reaction intermediates and transition states is examined and found important in order to predict reliable energetics.

Lackner K.S.

Cossi M., Scalmani G., Rega N., Barone V.

The polarizable continuum model (PCM), used for the calculation of molecular energies, structures, and properties in liquid solution has been deeply revised, in order to extend its range of applications and to improve its accuracy. The main changes effect the definition of solute cavities, of solvation charges and of the PCM operator added to the molecular Hamiltonian, as well as the calculation of energy gradients, to be used in geometry optimizations. The procedure can be equally applied to quantum mechanical and to classical calculations; as shown also with a number of numerical tests, this PCM formulation is very efficient and reliable. It can also be applied to very large solutes, since all the bottlenecks have been eliminated to obtain a procedure whose time and memory requirements scale linearly with solute size. The present procedure can be used to compute solvent effects at a number of different levels of theory on almost all the chemical systems which can be studied in vacuo.

Munshi P., Main A.D., Linehan J.C., Tai C., Jessop P.G.

A trace amount of alcohol cocatalyst and a stoichiometric amount of base are required during the hydrogenation of CO(2) to formic acid catalyzed by ruthenium trimethylphosphine complexes. Variation of the choice of alcohol and base causes wide variation in the rate of reaction. Acidic, nonbulky alcohols and triflic acid increase the rate of hydrogenation an order of magnitude above that which can be obtained with traditionally used methanol or water. Similarly, use of DBU rather than NEt(3) increases the rate of reaction by an order of magnitude. Turnover frequencies up to 95,000 h(-1) have now been obtained, and even higher rates should be possible using the cocatalyst and amine combinations identified herein. Preliminary in situ NMR spectroscopic observations are described, and the possible roles of the alcohol and base are discussed.

Takimoto M., Shimizu K., Mori M.

[reaction: see text]. Nickel-promoted alkylative or arylative carboxylation of terminal alkynes via a carbon dioxide fixation process was investigated. In the presence of a stoichiometric amount of a zero-valent nickel complex, the reaction of alkynes with CO2 gave a nickelacycle, which was reacted with various organozinc reagents under very mild conditions to provide beta,beta'-disubstituted, alpha,beta-unsaturated carboxylic acids in a highly regio- and stereoselective manner.

Arakawa H., Aresta M., Armor J.N., Barteau M.A., Beckman E.J., Bell A.T., Bercaw J.E., Creutz C., Dinjus E., Dixon D.A., Domen K., DuBois D.L., Eckert J., Fujita E., Gibson D.H., et. al.

The goal of the "Opportunities for Catalysis Research in Carbon Management" workshop was to review within the context of greenhouse gas/carbon issues the current state of knowledge, barriers to further scientific and technological progress, and basic scientific research needs in the areas of H2 generation and utilization, light hydrocarbon activation and utilization, carbon dioxide activation, utilization, and sequestration, emerging techniques and research directions in relevant catalysis research, and in catalysis for more efficient transportation engines. Several overarching themes emerge from this review. First and foremost, there is a pressing need to better understand in detail the catalytic mechanisms involved in almost every process area mentioned above. This includes the structures, energetics, lifetimes, and reactivities of the species thought to be important in the key catalytic cycles. As much of this type of information as is possible to acquire would also greatly aid in better understanding perplexing, incomplete/inefficient catalytic cycles and in inventing new, efficient ones. The most productive way to attack such problems must include long-term, in-depth fundamental studies of both commercial and model processes, by conventional research techniques and, importantly, by applying various promising new physicochemical and computational approaches which would allow incisive, in situ elucidation of reaction pathways. There is also a consensus that more exploratory experiments, especially high-risk, unconventional catalytic and model studies, should be undertaken. Such an effort will likely require specialized equipment, instrumentation, and computational facilities. The most expeditious and cost-effective means to carry out this research would be by close coupling of academic, industrial, and national laboratory catalysis efforts worldwide. Completely new research approaches should be vigorously explored, ranging from novel compositions, fabrication techniques, reactors, and reaction conditions for heterogeneous catalysts, to novel ligands and ligation geometries (e.g., biomimetic), reaction media, and activation methods for homogeneous ones. The interplay between these two areas involving various hybrid and single-site supported catalyst systems should also be productive. Finally, new combinatorial and semicombinatorial means to rapidly create and screen catalyst systems are now available. As a complement to the approaches noted above, these techniques promise to greatly accelerate catalyst discovery, evaluation, and understanding. They should be incorporated in the vigorous international research effort needed in this field.

Khamrai A., Ghosh S., Ganesh V.

Nickel catalysis has experienced a renaissance over the past two decades, driven by its ability to access diverse oxidation states (0 to +4). This review consolidates the advancements in nickel chemistry at its various oxidation states.

Kang C., Kim S., Han W., Ryu H., Seong W., Kim J., Park D., Park S., Park K., Park H.M., Kim H.T., Lee C.H., Hong S.

Kunihiro K., Rajeshkumar T., Maron L., Heyte S., Paul S., Roisnel T., Carpentier J., Kirillov E.

Kuznetsov Nikolai Yu., Maximov Anton L., Beletskaya Irina P.

The development of atom-economical and efficient processes for obtaining a variety of chemical products using CO2 as C1-synthon plays an increasingly important role in modern scientific and technological research. Due to the inertness of CO2 many extremely attractive routes to valuable chemical products turn out to be impossible to implement, particularly for thermodynamic reasons, leaving one only dreaming about them as something unattainable. This review demonstrates how the catalytic coupling of ethylene and CO2 into acrylic acid, once considered a "dream reaction" has not only become a reality, but has also evolved into the category of technological processes. The key stages of the long-term development of this unique reaction from the discovery of metal activation of CO2 and stoichiometric preparation of metallalactones to catalytic synthesis using a variety of metal-catalysts (Ni, Pd, Ru, Rh) showcase the ingenuity and skill of researchers as well as an example of consistent development in this field of chemistry. We believe that this remarkably successful example will inspire scientists to tackle any "impossible" problems.The bibliography includes 117 references.

Maity N., Garcia N., Jaseer E.A., Barman S., Aitani A.M., Tijani M.M., Al-Yassir N.

Catalytic CO2 conversion has always been a fascinating area of research in chemistry. CO2 being a highly abundant and commercially cheap carbon feedstock, it is immensely appealing if such conversion could be advanced to novel economical and sustainable routes to take over the existing industrial processes for accessing highly demanding organic products. Acrylic acid is produced industrially by two-step catalytic processes involving partial oxidation of propylene. Catalytic acrylic acid production by a direct oxidative C–C coupling between olefin and CO2 has remained a great challenge for the research community due to unfavorable thermodynamics. However, reactions conducted in the presence of a suitable base leading to the acrylate product were envisaged to shed some light on this end. Indeed, this domain of exploration has gained significant interest, especially towards achieving a direct catalytic carboxylation of ethylene by CO2. While several earlier reviews probed into catalyst systems associated with this research, the recently surfaced promising catalysts remained unaddressed. These developments provide vital insights for designing high-performance materials in intentional applications and commercial technologies for catalytic acrylate production. Examining these developments creates an opportunity for more sustainable processes, utilizing CO2 as a C1 feedstock, contributing significantly to the circular carbon economy. This review explores the latest advancements, offering a comprehensive overview of the gradual evolution of catalyst systems, and identifying optimal candidates for intentional applications. Special attention is given to proposed reaction mechanisms supported by theoretical studies, enhancing understanding of reaction cycles and suggesting new strategies for better catalyst systems.

Schaub T.

Natriumacrylat ist ein wertvoller Monomer für die Synthese von Superabsorbern und wird industriell in großem Maßstab hergestellt. Derzeit wird Natriumacrylat durch die Oxidation von Propen zu Acrylsäure und anschließende Neutralisation mit NaOH hergestellt. Die Synthese von Natriumacrylat aus CO2, Ethylen und NaOH wäre aufgrund der geringeren Rohstoffkosten sehr attraktiv, war aber viele Jahre lang nur eine „Traumreaktion“. Seit dem ersten Bericht im Jahr 2012 über ein katalytisches System für diese Synthese wurden erhebliche Fortschritte erzielt. Verschiedene Nickel- und Palladiumkatalysatoren wurden identifiziert. Darüber hinaus wurde der Einfluss der Base in dieser Reaktion bewertet. Die Verwendung von Lösungsmitteln, die bestimmte Kriterien erfüllen, ist für die Gestaltung von kontinuierlichen Prozesskonzepten notwendig. Bis heute haben sich zwei Prozesskonzepte ergeben: eines mit Phenolatbasen und das andere mit Alkoxidbasen.

Nguyen Q.P., Masood Z., Wang B.

Direct coupling of CO2 and ethylene (hereinafter DCCE) to acrylic acid is valuable for valorizing CO2 to manufacture acrylate-derived products. However, previous studies in DCCE have been limited on molecular catalysts with challenges in improving catalytic performance. In this work, we employed density functional theory calculations and ab initio molecular dynamics simulations to investigate the heterogeneous catalysis of DCCE over atomically dispersed metal centers at nitrogen-doped zigzag edge of graphene. Based on competitive adsorption and structural stability, Mo, Cr, V, Ru, and Ni active sites are chosen to explore the reaction kinetics. We find that the activation barriers are determined by the charge redistribution at transition states, which explains the trend of activity for the C-C coupling and the hydrogen transfer, two key steps in DCCE. Furthermore, we show that the intramolecular hydrogen transfer (rate-limiting step) is hindered due to the lack of local coordinate at the active sites. We thus propose to use co-adsorbed water as a "proton-exchanger" following a water-assisted route, and show that the activation barriers are reduced over all metal centers. Particularly, water promotes the hydrogen transfer over metals with strong CO2-ethylene co-activation and facile C-C coupling kinetics, which could be considered promising for DCCE. In both mechanisms, the stability of metallactone intermediate can be used to predict the catalytic activity. It is anticipated that the insights from this work can provide guidelines for mimicking well-defined multifunctional active sites in molecular catalysts to design heterogeneous catalysts for such C-C coupling, which advances catalytic utilization of CO2.

Zhu Y., Mu Y., Shen H., Sun L., Zeng Z., Liu Z.

The oxidative coupling of CO2 and ethylene for synthesizing acrylic acid and its derivatives is considered one of the "dream reactions" in catalysis. The formation of acrylic acid by CO2/C2H4 coupling is hardly possible due to the endothermic nature of the reaction. This work reports a comprehensive study of the nickelalactone formation from CO2/C2H4 coupling over Ni-catalysts. We have evaluated the accuracy of the DLPNO-CCSD(T) method in determining the barrier heights and the reaction energetics for the nickelalactone formation. Extrapolation to the complete basis set limit was performed using two-point extrapolation methods. It was found that the DLPNO-CCSD(T) method, in combination with the complete basis set cc-pVTZ/cc-pVQZ extrapolation, gives the error within 1.0 kcal/mol. To gain a molecular understanding of the formation of acrylic acid by CO2/C2H4 coupling, the distortion-interaction model was used as an energy decomposition method to analyze the inner- and outer-sphere reaction transition states, considering two competing pathways. It was found that i) the inner-sphere reaction is superior to the outer-sphere reaction owing to the lower distortion energy and stronger interactions, ii) three prominent pairs of orbital interactions exist between the Ni-C2H4 complex and the CO2 molecule, and iii) the dispersion correction is crucial to obtaining reliable non-covalent interaction energies.

Masood Z., Nguyen Q.P., Wang B.

Ding X., Mu Y., Zhu Y., Guo X., Liu K., Sun L., Liu Z.

Since the 1980s, nickel/palladium-based catalysts have been extensively studied for the coupling reactions of CO2 and ethylene. In this study, the CO2 and ethylene coupling mediated by the iron(0)-based catalyst with a bis(dicyclohexylphosphino)ethane (dcpe) ligand was systematically investigated by means of DFT calculations. The DFT functionals were first subjected to a benchmark test in order to describe an iron-catalyzed reaction with a two-state reactivity (TSR). For the Fe/dcpe catalytic system, the formation of the five-membered iron-lactone 3 follows a stepwise route, which is easy to occur with a low energy barrier of 13.8 kcal/mol. The competing reactions by CO2 insertion and β-H elimination determine the fate of the five-membered iron-lactone 3, which may lead to the formation of three different products, including the formation of i) succinic acid, ii) iso-methylmalonic acid, and iii) acrylic acid. The calculated TOFs showed that CO2 insertion into the five-membered iron-lactone 3 is more likely to occur (1.67 h−1 for the formation of succinic acid) compared with the β-H elimination leading to iso-methylmalonic acid and acrylic acid. Interestingly, β-H elimination can be effectively facilitated by addition of the electrophiles, and a comparable TOF of 0.042 h−1 was obtained for the formation of methyl acrylate in the presence of CH3I. Unlike nickel-/palladium-catalyzed CO2 and ethylene coupling reactions, all four iron(0)-catalyzed reaction routes investigated herein showed a two-state reactivity scenario involving spin crossover between triplet and quintet PESs. This study provides a mechanistic understanding of the intriguing iron(0)-catalyzed CO2 and ethylene coupling reactions, which may shed some light on the development of green catalysts for CO2 utilization.

Dahy A.A., Koga N.

Faba L., Rapado P., Ordóñez S.

Li R., Yang C., Niu B., Li L., Ma J., Li Z., Jiang H., Cheng W.

A Ni-catalyzed C–heteroatom cross-coupling of aryl halides is reported by employing photoinduced LMCT with DBU. The reaction proceeds under visible light irradiation without an external photosensitizer and involves a variety of nucleophiles.

Liu Z., Sun L., Ding X., Zhu Y.

Wagner C.L., Diao T.

This chapter documents nickel aryl and alkyl complexes. The complexes are organized by their supporting ligands such as tridentate, bidentate and monodentate ligands. Pincer ligands stabilize a variety of organonickel complexes that have enabled fundamental studies, but often lack catalytic reactivity. A variety of bidentate ligands have found applications in olefin polymerization and cross-coupling reactions. Monodentate NHC and phosphine ligands can support low-coordinate nickel complexes. The past two decades have witnessed the advancements in low-valent, high-valent, and mixed-valent nickel complexes. Monovalent nickel complexes can activate electrophiles to generate radicals, which is relevant to their catalytic reactivity. High-valent nickel complexes can mediate facile reductive elimination to form various bonds. Several monometallic and multimetallic nickel complexes serve as the biomimetic model of nickel-containing metalloenzymes and exhibit relevant reactivity. Ligand redox-activity and metal-ligand cooperativity are common methods for tuning the reactivity of nickel complexes.