CO Insertion Research Articles

Pd/PVP‐ Catalyzed Formylation of Amines and Nitroarenes to N‐Formamides with CO2 and Dimethylamine Borane: The Influence of CO2 on the Formation of Azoxyarenes

AbstractThe reactivity of dimethylamine borane (DMAB) towards amines and nitroarenes was investigated in the presence of the CO2 and Pd/PVP (PVP=polyvinylpyrrolidone) nanocatalyst. The formation of borane formate, Me2NH.BH2(OCHO), by the insertion of CO2 into the B−H bond was evidenced by NMR. The reaction of DMAB with CO2 also produced a second product, DMF, formed via self‐formylation. In the presence of aromatic or aliphatic amines corresponding N‐formamides were formed efficiently. Under the same conditions nitroarenes were hydrogenated to anilines or to azoxyarenes in the absence of CO2. In both reactions very high TOF values, up to 30 min−1, were obtained. Applying a higher excess of DMAB enabled the transformation of nitroarenes to N‐formamides. The Pd/PVP catalyst was used in 7 consecutive cycles of N‐methylaniline formylation with excellent selectivity and a total TON equal to 4700.

CH4 Carbonylation to Acetic Acid Using H2O as an Oxidant on a Rh-Functionalized UiO-67 Combined with Oriented External Electric Fields: Selectivity and Mechanistic Insights from DFT Calculations.

Acetic acid (CH3COOH), as an industrially important petrochemical product, is predominantly produced via multistep energy-intensive processes. The development of a rhodium single-site heterogeneous catalyst has received considerable attention due to its potential to transform CH4 into CH3COOH in a single step. Herein, the reaction mechanism for the generation of CH3COOH from CH4, CO, and H2O catalyzed by Rh-functionalized metal-organic framework (MOF) UiO-67 and the selectivity of products CH3COOH, formic acid (HCOOH), methanol (CH3OH), and acetaldehyde (CH3CHO) under the oriented external electric fields (OEEFs) were systematically explored by density functional theory (DFT) calculations. The results reveal that the insertion of CO into Rh-CH3 is the rate-determining step with a free energy barrier of 21.0 kcal/mol in CH4 carbonylation to CH3COOH. Upon applying an OEEF of Fx = +0.0050 au along the C-C bond, the rate-determining step shifts toward H2O decomposition with the barrier of 19.6 kcal/mol, significantly improving the selectivity for CH3COOH production, compared to the major competitive HCOOH route. The Brønsted-Evans-Polanyi (BEP) relationships between key transition states, field strength, and NPA charge transfer were established. This study may guide the rational design of atomically dispersed MOF catalysts for the selective coconversion of CH4 and CO to CH3COOH using H2O as the oxidant under the OEEF.

Computational design for enantioselective CO2 capture: asymmetric frustrated Lewis pairs in epoxide transformations.

Carbon capture and utilisation (CCU) technologies offer a compelling strategy to mitigate rising atmospheric carbon dioxide levels. Despite extensive research on the CO2 insertion into epoxides to form cyclic carbonates, the stereochemical implications of this reaction have been largely overlooked, despite the prevalence of racemic epoxide solutions. This study introduces an in silico approach to design asymmetric frustrated Lewis pairs (FLPs) aimed at controlling reaction stereochemistry. Four FLP scaffolds, incorporating diverse Lewis acids (LA), Lewis bases (LB), and substituents, were assessed via volcano plot analysis to identify the most promising catalysts. By strategically modifying LB substituents to induce asymmetry, a stereoselective catalytic scaffold was developed, favouring one enantiomer from both epoxide enantiomers. This work advances the in silico design of FLPs, highlighting their potential as asymmetric CCU catalysts with implications for optimising catalyst efficiency and selectivity in sustainable chemistry applications.

Physicochemical Analysis of Cu(II)-Driven Electrochemical CO2 Reduction and its Competition with Proton Reduction.

The reduction of CO2 has become a key role in reducing greenhouse gas emissions in efforts to search for long-term responses to climate change. We report a a couple of CO2-reducing molecular catalysts based on earth-abundant copper complexes. These are [Cu(DPA)(PyNAP)] (1) and [Cu(DPA)(PyQl)] (2) (where, DPA = pyridine-2,6-dicarboxylic acid, PyNAP = 2-(pyridin-2-yl)-1,8-naphthyridine, and PyQl = 2-(pyridin-2-yl)quinoline). The copper metal-catalysed 2-electron reduction of CO2 to CO in the presence of 2-protons is challenging. These catalysts exhibit the production of CO gas in DMF/water mixtures, achieving an impressive faradaic efficiency of 84% and 72% for complex 1 and 2 at -1.7 V vs. SCE, respectively, for selective CO2 reduction. The production of H2 due to 2H+ + 2e- was also observed as a byproduct through the competitive proton reduction reaction. This was cross-verified by online gas and mass analysis.Our investigations confirmed the stability of the electrocatalysts under the electrocatalytic conditions. The mechanistic pathways were proposed to work with the EECC and ECEC (E: electrochemical and C: chemical) mechanisms. A CO2 insertion into an in-situ generated hydride from the Cu-center generates CO through the favourable path.

Cascade CO2 Insertion in Carbanion Ionic Liquids Driven by Structure Rearrangement.

The CO2 chemisorption in state-of-the-art sorbents based on oxide/hydroxide/amine moieties is driven by strong chemical bonding formation in the carbonate/bicarbonate/carbamate products, which in turn leads to high energy input in sorbent regeneration. In addition, the CO2 uptake capacity was limited by the active sites' utilization efficiency, with each active site incorporating one CO2 molecule or less. In this work, a new concept and generation of sorbent was developed to achieve cascade insertion of multiple CO2 molecules by leveraging structure rearrangement as the driving force, leading to in situ generation of extra CO2-binding sites and significantly reduced energy input for CO2 release. The designed ionic liquids (ILs) containing carbanions with conjugated and asymmetric structure, deprotonated (methylsulfonyl)acetonitrile ([MSA]) anion, allowed the cascade insertion of two CO2 molecules via consecutive C-C and O-C bond formations. The proton transfer and structure rearrangement of the carboxylic acid intermediates played critical roles in stabilizing the first integrated CO2 and generating extra electron-rich oxygen sites for the insertion of the second CO2. The structure variation and reaction pathway were confirmed by operando spectroscopy, magnetic resonance spectroscopy (NMR), mass spectroscopy, and computational chemistry. The energy input in sorbent regeneration could be further reduced by harnessing the phase-changing behavior of the carbanion salts in ether solutions upon reacting with CO2, avoiding the energy consumption in heating the solvent. The fundamental insights obtained herein provide a promising approach to greatly improve the CO2 sorption performance via sophisticated molecular-scale structural engineering of the sorbents.

Reductive‐Transmetalation Reactions of ZnR2/(AlCp*)4 Heterobimetallic Combinations and Application Towards CO2 Insertion

AbstractOrgano‐aluminum compounds are usually derived via salt metathesis reactions starting from aluminum halides and s‐block organometallics such as organolithiums or Grignard reagents. Herein, an alternative route is reported using an Cp*Al(I)/Zn(II)R2 (Cp* = C5Me5; R = aryl) system which facilitates the formation of a range of halide and donor free heteroleptic triorgano‐alanes of the general formula [Al(Cp*)R2]. Exposing the obtained alanes to an atmosphere of CO2 enables for the selective insertion of CO2 in their AlCp* moieties. State of the art quantum chemical calculations support experimental observations providing mechanistic insights on the observed reactivity of the [Al(Cp*)R2] compounds towards this unsaturated organic molecule.

Effect of transition and alkali metals on Mo2C/Al2O3 catalysts for syngas to higher alcohols

Direct production of higher alcohols remains a great challenge in syngas conversion process. Herein, MMo2C/Al2O3 and KMMo2C/Al2O3 catalysts promoted by different transition metals M (M=Co, Fe, Cu, Ni, Zn, Nb) and alkali metal (K) were prepared by impregnation method to investigate the effect on CO hydrogenation to higher alcohols under milder reaction conditions (300°C, 3.0 MPa). The catalysts were characterized with XRD, H2-TPR, and XPS. It was found that the addition of transition metals and K resulted in the decrease of low-valent Mo species on the catalyst surface, which facilitated the generation of Mo4+ during the reaction. Increase in Mo4+ content facilitates the conversion of CO to CO*, which provides more CO insertion sites for the generation of alcohols. Moreover, the introduction of K also enhances the interaction of transition metals with Mo, which accelerates the formation of alcohols in the reaction. Meanwhile, the transition metal and Mo2C work together to promote the dissociative adsorption of CO. The production of higher alcohols is facilitated by the synergistic effect of the two mentioned above. Overall, the KCoMo/Al2O3 and KFeMo/Al2O3 catalysts exhibited high selectivity for higher alcohols, reaching 73.9 % and 71.3 % for C2+OH in the alcohol products, respectively. CO conversion of KFeMo/Al2O3 catalyst can reach 84.9 % with excellent stability in the reaction. Moreover, the possible pathways of the reaction were obtained by in-situ DRIFT characterization.

Linear Free Energy Relationships Associated with Hydride Transfer From [(6,6'-R2-bpy)Re(CO)3H]: A Cautionary Tale in Identifying Hydrogen Bonding Effects in the Secondary Coordination Sphere.

Six rhenium hydride complexes, [(6,6'-R2-bpy)Re(CO)3H] (bpy = 2,2'-bipyridine, R = OEt, OMe, NHMe, Me, F, Br), were synthesized. These complexes insert CO2 to form rhenium formate complexes of the type [(6,6'-R2-bpy)Re(CO)3{OC(O)H}]. All the rhenium formate species were characterized using X-ray crystallography, which revealed that the bpy ligand is not coplanar with the metal coordination plane containing the two nitrogen donors of the bpy ligand but tilted. A solid-state structure of [(6,6'-Me2-bpy)Re(CO)3H] determined using MicroED also featured a tilted bpy ligand. The kinetics of CO2 insertion into complexes of the type [(6,6'-R2-bpy)Re(CO)3H] were measured experimentally and the thermodynamic hydricities of [(6,6'-R2-bpy)Re(CO)3H] species were determined using theoretical calculations. A Brønsted plot constructed using the experimentally determined rate constants for CO2 insertion and the calculated thermodynamic hydricities for [(6,6'-R2-bpy)Re(CO)3H] revealed a linear free energy relationship (LFER) between thermodynamic and kinetic hydricity. This LFER is different to the previously determined relationship for CO2 insertion into complexes of the type [(4,4'-R2-bpy)Re(CO)3H]. At a given thermodynamic hydricity, CO2 insertion is faster for complexes containing a 6,6'-substituted bpy ligand. This is likely in part due to the tilting observed for systems with 6,6'-substituted bpy ligands. Notably, the 6,6'-(NHMe)2-bpy ligand could in principle stabilize the transition state for CO2 insertion via hydrogen bonding. This work shows that if only the rate of CO2 insertion into [(6,6'-(NHMe)2-bpy)Re(CO)3H] is compared to [(4,4'-R2-bpy)Re(CO)3H] systems, the increase in rate could be easily attributed to hydrogen bonding, but in fact all 6,6'-substituted systems lead to faster than expected rates.

Hydrophobic surface modification and morphology tuning of supported KNiMoS-based catalyst for synergistically enhanced higher alcohols synthesis via CO hydrogenation

MoS2-based catalysts have gained significant attention in higher alcohols synthesis (HAS) via CO hydrogenation. However, the water–gas shift (WGS) to produce CO2 in HAS is undesirable reaction, which will reduce the efficiency of carbon utilization. Here, we provide a facile strategy with hydrophobic surface modification and metal-support interaction modulation to design a series of KNiMoS/MgAl catalysts. The organic modified SiO2 shell with excellent hydrophobicity effectively shortens the residence of water formed in HAS, and further suppress the generation of CO2 and low-chain hydrocarbons. Moreover, the moderate metal-support interaction between MoS2-based active species and MgAl support can regulate the dispersion and sulfidation extent of MoS2 slabs to provide more active sites for alcohol formation. The MoS2 slabs with predominant double-layer structure enhance the C–C propagation and CO insertion in HAS. And as a result, the optimal KNiMoS/MgAl@Si(c)-5 achieves total alcohols selectivity of 74.7 %, C2+OH selectivity of 85.8 % in total alcohols, and C2+ alcohols space–time yield of 107.8 mg gcat-1h−1, where C2+ alcohols space–time yield is 3.50 and 2.71 times than those on KNiMoS/MgAl(H) and KNiMoS/MgAl, respectively. Notably, the total selectivity of CO2 and hydrocarbons is less than 23.2 %, and selectivity ratio of C2-4OH to methanol can be overturned from 1.9 to 6.0. The dependence of HAS performance on the morphology of MoS2 slabs were also demonstrated to get insight into the structure-performance relationship. This work provides a facile strategy with tunable hydrophobic surface and metal-support interaction of MoS2-based catalysts for further improvement of catalytic performance.

Effect of backbone linker (O vs NH) on the ability of pincer-supported nickel hydrides to reduce CO2

The reactivity of nickel hydrides supported by a pincer ligand often can be tuned by modifying the ligand at the three donor sites. In this study, ligand modification is made at the backbone, more specifically the linkers X and Y in {2,6-C6H3(XPtBu2)(YPtBu2)}NiH. Of the three nickel hydrides investigated herein, the PNCNP-pincer complex (X = Y = NH) is the most reactive one towards CO2, whether it is for the rate of CO2 capture from air or for the thermodynamic favorability of CO2 insertion into the Ni–H bond. The POCOP-pincer complex (X = Y = O) is the least reactive hydride whereas the POCNP-pincer complex (X = O, Y = NH) is ranked in the middle. To have access to the hybrid pincer complex, an improved synthetic method for the proligand, m-C6H4(OPtBu2)(NHPtBu2), is also developed.

Kinetic Studies of CO2 Insertion into Metal-Element σ-Bonds.

ConspectusDespite the plethora of metal catalyzed reactions for CO2 utilization that have been developed in academic laboratories, practical systems remain elusive. The understanding of the elementary steps in catalysis is a proven method to improve catalytic performance. In many catalytic cycles for CO2 utilization, the insertion of CO2 into a metal-element σ-bond, such as hydrides, alkyls, amides, or hydroxides, is a crucial step. However, despite the many demonstrations of CO2 insertion, there are a paucity of kinetic studies, and information about the reaction mechanism has been predominantly elucidated from computational investigations. In this Account, kinetic studies on CO2 insertion into late transition metal-element σ-bonds performed by my group are summarized, along with their implications for catalysis.A common pathway for CO2 insertion into a metal hydride involves a two-step mechanism. The first step is nucleophilic attack on CO2 by the hydride to generate an H-bound formate, followed by rearrangement to form an O-bound formate product. Kinetic studies on systems in which both the first and second steps are proposed to be rate-determining, known as inner-sphere and outer-sphere processes, respectively, show that insertion rates increase as (i) the ligand trans to the hydride becomes a stronger donor, (ii) the ancillary ligand becomes more electron-donating, and (iii) the Dimroth-Reichardt parameter of the solvent increases. However, the magnitude of these effects is generally smaller for inner-sphere processes because there is less buildup of charge in the key transition state. For similar reasons, the presence of Lewis acids only increases the rate of outer-sphere processes. These results suggest it may be possible to experimentally differentiate between inner- and outer-sphere processes.The insertion of CO2 into a metal-alkyl bond results in the formation of a C-C bond, which is important for the generation of fuels from CO2. For square planar Group 10 complexes, the presence of a strong donor ligand trans to the alkyl group is critical for kinetically promoting insertion. Further, the nucleophilicity of the alkyl ligand directly impacts the rate of CO2 insertion via an SE2 mechanism, as does the steric bulk of the complex, and the reaction solvent. In contrast to the relatively slow rates of insertion observed for metal alkyls, CO2 insertion is rapid for metal hydroxides and amides. Although kinetics trends could be determined for hydroxides, reactions with amides are too fast for quantitative studies.Overall, the rates of insertion correlate with the nucleophilicity of the element in the metal-element σ-bond, so amide > hydroxide > hydride > alkyl. Due to the related pathways for insertion, similar trends in ligand and solvent effects are observed for insertion into different metal-element σ-bonds. Thus, the same strategies can be used to control the rates of insertion across systems. Differences in the magnitude of solvent and ligand effects are caused by variation in the amount of charge build-up on the metal in the rate-determining transition state. Likely, given that CO2 is related to organic molecules such as aldehydes, ketones, and amides, the results described in this Account are general to a wider range of substrates.

Nitrogen-rich carbon nanosheets supported copper catalysts for oxidative carbonylation of ethanol

Two-dimensional (2D) nitrogen-rich carbon nanosheets NC-x with a nitrogen content of 5.2 %-6.8 wt% were characterized by a one-step co-pyrolysis method and employed as Cu catalyst supports for oxidative carbonylation of ethanol. Carbon nanosheets with abundant nitrogen defects were achieved by tuning the dosage of ammonium oxalate, in which the Cu/NC-12 catalyst performed excellent activity. Furthermore, Cu/NC-x catalysts presented significantly superior catalytic activity than that of copper/carbon nanosheets (Cu/C) catalyst, it can be ascribed to the most suitable nitrogen doping to promote the exposure and dispersion of Cu species and pyridine nitrogen served as the main anchor sites to increase the ratio of Cu+/(Cu++Cu0). Density functional theory calculations further proved that introducing nitrogen atoms into carbon nanosheets effectively reinforced binding to Cu4 and adsorption of intermediates with NC, and a remarkable activity on Cu/NC-12 was achieved by a more favorable insertion of CO in the rate-determining step.

A Data-Driven Approach for Enhanced CO2 Capture with Ruthenium Complexes.

To attain carbon neutrality, significant efforts have been made to capture and utilize CO2. The homogeneous hydrogenation of CO2 catalyzed by transition metal complexes, particularly the ruthenium complexes, has demonstrated significant advantages and is regarded as a viable approach for practical application. Insertion of CO2 into the Ru-H bond, producing the Ru-formate product, is the key step in the hydrogenation of CO2. In order to parameterize the catalytic activities in the CO2 insertion into the Ru-H bond, the concept of simplified mechanism-based approach with data-driven practice (SMADP) has been introduced in this paper. The results showed that the hydricity of the Ru-H complex (ΔGH-) might serve as a single active descriptor in the process of CO2 insertion, and that a novel ruthenium complex in CO2 catalysis may not be easily obtained by mere modification of the auxiliary ligand at the ruthenium metal site.

Preparation of silicon foam supported CoMn catalysts and their catalytic performances in higher alcohol synthesis via syngas

A series of silicon foam supported CoMn catalysts were prepared using impregnation, precipitation, and hydrothermal methods. Combining the characterization techniques such as XRD, H2-TPR, N2 physical adsorption, TEM, and XPS, the effect of different catalyst preparation methods on the catalytic performance in the synthesis of higher alcohols from syngas was investigated. It is shown that there are Co2+(Co2C) and Co0 species on the surface of the catalyst. The active sites of Co2C-Co0 on the surface of the catalyst prepared by hydrothermal method have a good synergistic effect, which is conducive to the generation of alcohols. A higher proportion of Co2C also promotes the associative adsorption and insertion of CO, resulting in the highest alcohol selectivity. Under the reaction conditions of t=260 °C, p=5.0 MPa, GHSV=4500 h–1 and H2/CO(volume ratio)=2:1, the catalyst exhibited the best reaction performances with CO conversion of 11.1%, total alcohol selectivity of 34.7%, and C2+OH selectivity of 34.5%.

The efficient and reusable imidazolium-organoboron catalysts for green CO2 insertion reactions in solvent-free under atmospheric and high-pressure conditions

Organoboron compounds that are available in industrial and scientific research were investigated as organocatalysts for the coupling reaction of CO2 into cyclic carbonates as fine chemicals in solvent-free and under sustainable green atmospheric and high-pressure conditions (1 atm and 1.6 MPa, 100 °C, 2 h). This work synthesized a series of imidazolium-organoboron catalysts (IBC1-IBC8) using the eco-friendly and metal-free methodology and characterized by various analysis techniques. These techniques were NMR (1H, 13C, and 11B), UV–Vis, FT-IR, Mass spectrometry, C/H/N analysis, and melting point measurement together with thermal gravimetric analysis (TGA-DTA), respectively. After that, the Lewis acidity of the synthesized imidazolium-organoboron catalysts, which is important for catalytic CO2 conversion studies, was investigated by the traditional Gutmann-Beckett test, and the Lewis acidity order of the target compounds was found at range 54.96–50.36 ppm. In the presence of 0.1 mol% imidazolium-organoboron catalyst (IBC8) and 0.2 mol% DMAP as co-catalyst, 4-chloromethyl-1,3-dioxalan-2-one was obtained as cyclic carbonate from epichlorohydrin in 44.9 % yield and 97.6 % selectivity (1 atm and 100 °C) and in an excellent 97 % yield with 98.9 % selectivity (1.6 MPa and 100 °C) in 2 h without any solvents. After the imidazolium-organoboron catalyst (IBC8) showed efficient catalytic conversion and high selectivity, the effect of different parameters, including the effect of substrate, Lewis acid-base, reaction time, reaction temperature, CO2 pressure, and catalyst amount, was studied for this catalyst. According to the obtained catalytic conversion results, it was also determined that the optimum Cat./ECH ratio for CO2 cycloaddition reactions is 1/1000.

Revisiting the Mechanism of Asymmetric Ni-Catalyzed Reductive Carbo-Carboxylation with CO2: The Additives Affect the Product Selectivity.

The mechanistic details of the asymmetric Ni-catalyzed reductive cyclization/carboxylation of alkenes with CO2 have been revisited using DFT methods. Emphasis was put on the enantioselectivity and the mechanistic role of Lewis acid additives and in situ formed salts. Our results show that oxidative addition of the substrate is rate-limiting, with the formed Ni(II)-aryl intermediate preferring a triplet spin state. After reduction to Ni(I), enantioselective cyclization of the substrate occurs, followed by inner sphere carboxylation. Our proposed mechanism reproduces the experimentally observed enantiomeric excess and identifies critical C-H/O and C-H/N interactions that affect the selectivity. Further, our results highlight the beneficial effect of Lewis acids on CO2 insertion and suggest that in situ formed salts influence if the 5-exo or 6-endo product will be formed.

Mechanistic insight into electrocatalytic CO2 reduction to formate by the iron(I) porphyrin complex: A DFT study

Electrocatalytic reduction of CO2 into value-added chemicals has been considered as a promising pathway to mitigate the energy crisis and global warming. Iron porphyrins have been extensively studied for electrocatalytic CO2 reduction reaction (CO2RR), known for their ability to promote CO2-to-CO conversion. However, the mechanism of CO2-to-HCOO− conversion by Fe porphyrin remains unclear. Here, by means of density functional theory (DFT) calculations, we investigated the detailed mechanism of a novel Fe porphyrin catalyst for CO2 reduction to HCOO− in its Fe(I) state. Our results demonstrated that the reduction of CO2 to HCOO− proceeds via the C-protonation of an FeII-OCO•− complex, rather than through the hydrolysis of an FeIII-COOH complex or CO2 insertion in an Fe−H bond. Furthermore, the FeIII-COOH complex is found to be a unstable intermediate. Protonation of its hydroxyl group, accompanied by C−OH bond cleavage to produce CO, is both thermodynamically and kinetically unfeasible. Instead, the FeIII-COOH complex undergoes a coordination switch followed by a conformational change to form the active FeII-OCO•− complex, which promotes the production of HCOO−. Moreover, the single-electron reduction of FeIII-COOH gives FeII-COOH, leading to formation of CO rather than HCOO−. The insights gained from this study may contribute to design of electrocatalysts for selective CO2 reduction to formate.

Highly efficient capture and conversion of CO2 into cyclic carbonates from actual flue gas under atmospheric pressure

Chemical conversion of CO2 to cyclic carbonates is one of the most attractive strategies for CO2 capture and storage utilization. Herein, a binary organocatalyst of 3-aminobenzylalcohol/n-Bu4NI was used to gently catalyze the insertion of CO2 into the terminal/internal epoxides to generate cyclic carbonates under metal-free and solvent-free conditions. Twelve representative terminal epoxides reacted with CO2 to achieve excellent cyclic carbonate yields of up to 98.3 % at 30 °C and 1 atm CO2 and six low activity internal di-substituted epoxides were converted to corresponding cyclic carbonates with yields of up to 96.2 %. Experiments on actual flue gas and water resistance revealed the potential industrial value of this binary organocatalyst. The yield of cyclic carbonate reached 99 % by using actual flue gas under very mild conditions of 60 °C and 1 atm. The results of 4-fold epoxide amplification experiment showed that the residual CO2 in the flue gas was only 793 ppm after reaction at 1 atm and 60 °C, indicating the good CO2 capture and conversion ability. Reaction kinetics and catalytic mechanism of the cycloaddition were investigated in detail. The synergistic effect among functional groups of catalysts on substrates is the essential factor for the high activity of the catalyst.

Synthesis and Reactivity of Dipalladated Derivatives of Terephthalaldehyde.

The polynuclear complex [{μ-C1,C4,N,N″-C6H2{C(H)=N(nBu)}2-2,5}{Pd(μ-OAc)}]2 (I) reacts with tbbpy (4,4'-di-tert-butyl-2,2'-bipyridine) and TlOTf to form the dinuclear complex [{μ-C1,C4,N,N″-C6H2{C(H)=N(nBu)}2-2,5}{Pd(tbbpy)}2] (1). The hydrolysis of I with acetic acid in a 5:1 acetone/water mixture, in the presence of two equivalents of tbbpy and excess NaX (X = Br, I), yields the dipalladated terephthalaldehyde complexes [C6H2{PdX(tbbpy)}2-1,4-(CHO)2-2,5] [X = Br (2a), X = I (2b)], which are the first fully characterized complexes of this type. The reaction of 2a,b with CO results in the insertion of CO into both aryl-Pd bonds, forming [C6H2{C(O){PdX(tbbpy)}}2-1,4-(CHO)2-2,5] [X = Br (3a), X = I (3b)], which are the first examples of complexes with CO inserted into two separate aryl-metal bonds involving the same ligand. The bromo complex 2a reacts with excess XylNC in acetone, causing the precipitation of the dinuclear complex 2,3,6,7-tetrahydrobenzo[1,2-c:4,5-c']dipyrrole-1,5-dione-2,6-dixylyl-3,7-bis{=C(NHXyl)-C(=NXyl)-[PdBr(CNXyl)2]} (4), which is the result of the insertion of three molecules of the isocyanide into each aryl-Pd bond and the nucleophilic attack of one of them at each formyl group. When complex 4 reacts with TlOTf and residual water in 1,2-dichloroethane at 70 °C, depalladation occurs, and the organic compound 2,3,6,7-tetrahydrobenzo[1,2-c:4,5-c']dipyrrole-1,5-dione-2,6-dixylyl-3,7-bis{=C(NHXyl)-C(O)NHXyl} (5) can be isolated. The crystal structures of 1·4CHCl3, 4·2CH2Cl2·3hexane, and 5·2CDCl3 have been determined by X-ray crystallography.

Differential Activation of Alkynes between Capped and Naked Ag Nanoclusters Anchored by Highly-Open Mesoporous CeO2 for Two Coupling Reactions with CO2.

The cyclization of 3-hydroxy alkynes and the carboxylation of terminal alkynes both with CO2 are two attractive strategies to simultaneously reduce CO2 emission and produce value-added chemicals. Herein, the differential activation of alkynes over atomically precise Ag nanoclusters (NCs) supported on Metal-organic framework-derivedhighly-open mesoporous CeO2 (HM-CeO2) by reserving or removing their surface captopril ligands is reported. The ligand-capped Ag NCs possess electron-rich Ag atoms as efficient π-activation catalytic sites in cyclization reactions, while the naked Ag NCs possess partial positive-charged Ag atoms as perfect σ-activation catalytic sites in carboxylation reactions. Impressively, via coupling with HM-CeO2 featuring abundant basic sites and quick mass transfer, the ligand-capped Ag NCs afford 97.9% yield of 4,4-dimethyl-5-methylidene-1,3-dioxolan-2-one for the cyclization of 2-methyl-3-butyn-2-ol with CO2, which is 4.5 times that of the naked Ag NCs (21.7%), while the naked Ag NCs achieve 98.5% yield of n-butyl 2-alkynoate for the carboxylation of phenylacetylene with CO2, which is 15.6 times that of ligand-capped Ag NCs (6.3%). Density functional theory calculations reveal the ligand-capped Ag NCs can effectively activate alkynyl carbonate ions for the intramolecular ring closing in cyclization reaction, while the naked Ag NCs are highly affiliative in stabilizing terminal alkynyl anions for the insertion of CO2 in carboxylation reaction.