Catalytic Relevance Research Articles

Metal-Ligand Covalency in the Valence Excited States of Metal Dithiolenes Revealed by S 1s3p Resonant Inelastic X-ray Scattering.

Metallo dithiolene complexes with biological and catalytic relevance are well-known for having strong metal-ligand covalency, which dictates their valence electronic structures. We present the resonant sulfur Kβ (1s3p) X-ray emission spectroscopy (XES) for a series of Ni and Cu bis(dithiolene) complexes to reveal the ligand sulfur contributions to both the occupied and unoccupied valence orbitals. While S K-edge X-ray absorption spectroscopy played a critical role in identifying the covalency of the unoccupied orbitals of metal dithiolenes, the present focus on XES explores the occupied density of states. For a series of [Cu(mnt)2]n- and [Ni(mnt)2]n- anions and dianions, a comparison of the nonresonant and resonant S Kβ XES spectra highlights the dramatic improvement in spectral resolution and corresponding ability to differentiate subtle changes in occupied electronic structure across the series. Furthermore, the use of resonant inelastic X-ray scattering (RIXS) probes the valence excited states and the core-valence couplings of the complexes. By employing a theoretical approach based on time-dependent density functional theory to interpret the RIXS spectra, we reveal how metal-ligand covalency influences the excited state energies and covalencies. We identify the low energy excited states as having the same symmetry as the nominal "ligand field" or "d-d" states that typically dominate the photophysics of 3d metal complexes but with significant metal-ligand charge transfer character dictated by their covalency. These results suggest that strong metal-ligand covalency can be used to influence the charge-transfer photochemistry of first row transition metal complexes.

Unusual S=1 Four‐Coordinate Fe(IV) Complexes Supported by Bisamide Ligands: Syntheses, Characterization, and Electronic Structures

AbstractThe catalytic relevance of Fe(IV) species in non‐heme iron catalysis has motivated synthetic advances in well‐defined five‐ and six‐coordinate Fe(IV) complexes for a better understanding of their fundamental electronic structures and reactivities. Herein, we report the syntheses of FeDipp2 and FeMes2, a pair of unusual four‐coordinate non‐heme formally Fe(IV) complexes with S=1 ground states supported by strongly donating bisamide ligands. By combining spectroscopic characterization and computational modeling, we found that small variations in ligand aryl substituents resulted in substantial changes in both structures and bonding. This work highlights the strong donor capabilities and modularity of the bisamide ligand set. More broadly, it is a critical contribution to the utilization of ligand design to modulate molecular geometries and electronic structures of low‐coordinate, high‐valent iron complexes.

Unusual S=1 Four-Coordinate Fe(IV) Complexes Supported by Bisamide Ligands: Syntheses, Characterization, and Electronic Structures.

The catalytic relevance of Fe(IV) species in non-heme iron catalysis has motivated synthetic advances in well-defined five- and six-coordinate Fe(IV) complexes for a better understanding of their fundamental electronic structures and reactivities. Herein, we report the syntheses of FeDipp2 and FeMes2, a pair of unusual four-coordinate non-heme formally Fe(IV) complexes with S=1 ground states supported by strongly donating bisamide ligands. By combining spectroscopic characterization and computational modeling, we found that small variations in ligand aryl substituents resulted in substantial changes in both structures and bonding. This work highlights the strong donor capabilities and modularity of the bisamide ligand set. More broadly, it is a critical contribution to the utilization of ligand design to modulate molecular geometries and electronic structures of low-coordinate, high-valent iron complexes.

Para-Hydroxy Ni(II)-POCOP Pincer Complexes as Modifiers on Carbon Paste Electrodes and Their Application in Methanol Electro-Oxidation in Alkaline Media

The application of organometallic materials as anodes in fuel cell devices has experienced a notable increase in recent years. However, the use of POCOP pincer complexes remains scarcely explored despite their great relevance in catalysis. Thus, in this work, the electrocatalytic activity to methanol in alkaline media of three Ni(II)-based POCOP pincer complexes—[NiCl{C6H2-4-OH-2,6-(OPiPr2)2}] (a1), [NiCl{C6H2-4-OH-2,6-(OPtBu2)2}] (a2), and [NiCl{C6H2-4-OH-2,6-(OPPh2)2}] (a3)—will be discussed. The complexes were use as modifiers of carbon paste electrodes that were evaluated using cyclic voltammetry considering diverse factors, such as the absence and presence of MeOH, diverse proportions (% w/w) of the complex in the electrode, scan rate, and different MeOH concentrations. Results indicated the presence of a redox pair Ni(II)/Ni(III) with a quasi-reversible behavior in all complexes, the anodic peak currents of which were proportional to the increase in MeOH concentrations (0.05–0.3 mM), and their oxidation potentials varied in the function of the P-substituent in the Ni(II)-POCOPs backbone. Complex a1 exhibited the best current density (429.5 mA cm2 at 0.5 mM) compared to its analogs a2 and a3. The current intensity of all electrodes displays good stability, which remains—with slight changes—up to 100 s. Moreover, a comparison of their catalytic rate constants suggested a great activity in complex a1 (0.52 × 106 cm3 mol−1 s−1) compared to its analogues, implying a great activity in the electro-oxidation of MeOH. Hence, this work opens new opportunities for the electrochemical application of POCOPs complexes for future DMFCs development.

Catalytically Relevant Organocopper(III) Complexes Formed through Aryl-Radical-Enabled Oxidative Addition.

Stepwise oxidative addition of copper(I) complexes to form copper(III) species via single electron transfer (SET) events has been widely proposed in copper catalysis. However, direct observation and detailed investigation of these fundamental steps remain elusive owing largely to the typically slow oxidative addition rate of copper(I) complexes and the instability of the copper(III) species. We report herein a novel aryl-radical-enabled stepwise oxidative addition pathway that allows for the formation of well-defined alkyl-CuIII species from CuI complexes. The process is enabled by the SET from a CuI species to an aryl diazonium salt to form a CuII species and an aryl radical. Subsequent iodine abstraction from an alkyl iodide by the aryl radical affords an alkyl radical, which then reacts with the CuII species to form the alkyl-CuIII complex. The structure of resultant [(bpy)CuIII(CF3)2(alkyl)] complexes has been characterized by NMR spectroscopy and X-ray crystallography. Competition experiments have revealed that the rate at which different alkyl iodides undergo oxidative addition is consistent with the rate of iodine abstraction by carbon-centered radicals. The CuII intermediate formed during the SET process has been identified as a four-coordinate complex, [CuII(CH3CN)2(CF3)2], through electronic paramagnetic resonance (EPR) studies. The catalytic relevance of the high-valent organo-CuIII has been demonstrated by the C-C bond-forming reductive elimination reactivity. Finally, localized orbital bonding analysis of these formal CuIII complexes indicates inverted ligand fields in σ(Cu-CH2) bonds. These results demonstrate the stepwise oxidative addition in copper catalysis and provide a general strategy to investigate the elusive formal CuIII complexes.

Cover Feature: Synergy Between Supported Metal Single Atoms and Nanoparticles and their Relevance in Catalysis (ChemCatChem 15/2023)

Cover Feature: Synergy Between Supported Metal Single Atoms and Nanoparticles and their Relevance in Catalysis (ChemCatChem 15/2023)

Synergy Between Supported Metal Single Atoms and Nanoparticles and their Relevance in Catalysis

AbstractCatalytic active sites consisting in isolated metal single atoms can be found in enzymatic, homogenous and heterogeneous catalysts. In heterogeneous catalysis, single‐atom catalysts (SACs) may offer high reactivity and selectivity towards some reactions provided their local coordination environment and electronic properties are correctly tuned. These sites generally possess specific properties compared to metal nanoparticles or clusters. Because of the difficulty, inherent in supported catalysis, of preparing catalysts having a high homogeneity of active sites, these two species have had to coexist in many supported catalysts. If the current trend is often limited to comparing the reactivity of these two types of species, we will see in this mini‐review that for few years, work has highlighted a possible synergy between these species to improve catalytic performance. The different types of synergies are discussed, as well as challenges and opportunities for such catalysts in thermal‐, electro‐ and photo‐catalysis.

Simultaneous Hydrogen Bonds with Different Binding Modes: The Acceptor "Rules" but the Donor "Chooses".

This computational work studies the different hydrogen bond (HB) binding modes that can be established between neighbouring HB donors and acceptors in structures with relevance in catalysis and biology. To analyse the electronic effect on the σ-hole, unsubstituted HB donors and ones with two different substituents, an electron withdrawing (EWG), and an electron donating (EDG) group, were studied. Upon complexation, three different binding modes were observed: bifurcated, parallel, and zigzag. It was found that, as a general trend, HBs within a parallel pattern are the strongest followed by those within bifurcated and zigzag binding modes, leading to a "competition" between the last two. Similar patterns and trends have been found in experimental structures found in a search within the CSD. In conclusion, even though the HB acceptors "rule" the pattern and strength of the HB interactions within the dimers, when there is an option for different binding modes within a particular dimer, the HB donors "choose" the type of binding established.

Characterization and analysis of ring topology of zeolite frameworks

The topology of zeolite frameworks and of associated tetrahedral sites (T-sites) are commonly characterized by their associated rings, typically defined as some set of closed paths or cycles through a framework that cannot be decomposed into shorter cycles. These ring descriptors have been used to identify feasible zeolite topologies, to describe the similarity and differences between zeolites, to identify sites or voids of catalytic relevance, and as machine learning fingerprints. Numerous definitions and algorithms for finding zeolite rings have been proposed and applied throughout the literature. Here we report an analysis of rings and T-sites in a large number of zeolite frameworks using Zeolite Simulation Environment, a Python package that implements an efficient algorithm presented by Goetzke and Klein for finding rings in arbitrary frameworks. We compare the result of a number of common and new ring definitions applied to a large number of common zeolite frameworks. We discover previously unrecognized rings in a number of frameworks. We show that the vertex symbol, a common approach used to characterize T-sites, misses important parts of the stereochemistry around a T-site, and propose an alternative definition. This tool provides an effective platform for characterizing zeolite and T-site structures useful for building models and doing machine learning.

Principles of DNA cleavage in CRISPR-Cas9.

At the core of the CRISPR-Cas9 genome-editing technology, the endonuclease Cas9 introduces site-specific breaks in double-stranded DNA. In this system, the catalysis of target DNA cleavage by the highly flexible HNH domain is undefined, with two possible conformations whose catalytic relevance has remained unmet. Here, extensive molecular simulations - harnessing multi-microsecond molecular dynamics, quantum mechanics and free energy approaches - are combined with solution NMR and DNA cleavage assays to establish how the HNH nuclease is activated and cleaves the target DNA. We show that the conformation of the active state is critically dependent on the presence of Mg2+, unveiling its cardinal structural role in the organization of the active site. Solution NMR, DNA cleavage assays and molecular simulations of the Mg2+-bound HNH report on the formation of this active state, and consistently show that the protonation state of catalytic H840 is strongly affected by residue mutations within the active site. Finally, quantum mechanical simulations establish that DNA cleavage occurs through the identified active state, showing that the catalysis is activated by H840 and completed by K866, in line with DNA cleavage experiments. Overall, high-level computations, supported by experimental evaluation, resolve the catalytic mechanism and which of the known HNH conformations is responsible for target DNA cleavage in CRISPR-Cas9. This information helps enhancing the catalytic efficiency of Cas9 and its specificity, furthering the development of genome-editing tools.

Improving and stabilizing fluorinated aryl borane catalysts for epoxide ring-opening

Epoxide ring-opening is a key reaction in organic chemistry. We have previously shown that B(C6F5)3, a strongly Lewis acidic arylborane, exhibited high rates and unusual selectivities for catalyzing the ring-opening of aliphatic epoxides with alcohols. Here we compare catalysts of the form B(C6H5−XFX)3 (x = 5, 4, 3, and 0) and determine that moderately Lewis acidic arylboranes have higher regioselectivity, but slower rates in this reaction. At high temperatures, these arylboranes can also hydrolyze into inactive species. However, deactivation is suppressed in the presence of co-catalytic amounts of 1,2-propanediol, and DFT calculations suggest a role for arylborane-H2O-diol complexes. Thermal stabilization and regioselectivity enhancement by diol are both more pronounced for B(C6F5)3 than for less Lewis acidic B(C6HF4)3 and B(C6H2F3)3 catalysts. These results further demonstrate the catalytic relevance of H-bound networks of arylboranes and diols and enable their use at higher temperatures and greatly increased rates.

Continuous Pyrolysis Microreactors: Hot Sources with Little Cooling? New Insights Utilizing Cation Velocity Map Imaging and Threshold Photoelectron Spectroscopy.

Resistively heated silicon carbide microreactors are widely applied as continuous sources to selectively prepare elusive and reactive intermediates with astrochemical, catalytic, or combustion relevance to measure their photoelectron spectrum. These reactors also provide deep mechanistic insights into uni- and bimolecular chemistry. However, the sampling conditions and effects have not been fully characterized. We use cation velocity map imaging to measure the velocity distribution of the molecular beam signal and to quantify the scattered, rethermalized background sample. Although translational cooling is efficient in the adiabatic expansion from the reactor, the breakdown diagrams of methane and chlorobenzene confirm that the molecular beam component exhibits a rovibrational temperature comparable with that of the reactor. Thus, rovibrational cooling is practically absent in the expansion from the microreactor. The high rovibrational temperature also affects the threshold photoelectron spectrum of both benzene and the allyl radical in the molecular beam, but to different degrees. While the extreme broadening of the benzene TPES suggests a complex ionization mechanism, the allyl TPES is in fact consistent with an internal temperature close to that of the reactor. The background, room-temperature spectra of both are superbly reproduced by Franck-Condon simulations at 300 K. On the one hand, this leads us to suggest that room-temperature reference spectra should be used in species identification. On the other hand, analysis of the allyl iodide pyrolysis data shows that iodine atoms often recombine to form molecular iodine on the chamber surfaces. Such sampling effects may distort the chemical composition of the scattered background with respect to the molecular beam signal emanating directly from the reactor. This must be considered in quantitative analyses and kinetic modeling.

Hydride state accumulation in native [FeFe]-hydrogenase with the physiological reductant H2 supports its catalytic relevance.

Small molecules in solution may interfere with mechanistic investigations, as they can affect the stability of catalytic states and produce off-cycle states that can be mistaken for catalytically relevant species. Here we show that the hydride state (Hhyd), a proposed central intermediate in the catalytic cycle of [FeFe]-hydrogenase, can be formed in wild-type [FeFe]-hydrogenases treated with H2 in absence of other, non-biological, reductants. Moreover, we reveal a new state with unclear role in catalysis induced by common low pH buffers.

One Decade of Computational Studies on Single-Atom Alloys: Is In Silico Design within Reach?

ConspectusSingle-Atom alloys (SAAs) are an emerging class of materials consisting of a coinage metal (Cu, Ag, and Au) doped, at the single-atom limit, with another metal. As catalysts, coinage metals are rarely very active on their own, but when they are, they exhibit high selectivity. On the other hand, transition metals are usually very active but not as selective. Incorporating transition metals (guest elements) into coinage metals (host material) is therefore appealing for combining the activity and selectivity of each constituent in a balanced way. Additionally, first-principles calculations have shown that single atoms embedded in the surface of a coinage metal can exhibit emergent properties. Here, we describe how computational studies based on density functional theory (DFT) and kinetic Monte Carlo (KMC) simulations, often undertaken in close collaboration with experimental research groups, have shaped, over the past decade, the way we understand SAA catalysis.This Account reviews our contributions in elucidating the stability of SAAs, their electronic structure, and the way adsorbates interact and react on SAA catalytic surfaces. By studying in detail the processes that affect the stability of the SAA phase, we have shown that out of several bimetallic combinations of coinage metals with prominent Pt-group metals only PtCu and PdCu are stable surface alloys under vacuum. However, more surface alloy structures are possible in the presence of adsorbates because the latter can stabilize, via strong binding, dopants in the surface of the material. More interestingly, a large number of these surface alloys are resistant to the aggregation of dopant atoms into clusters, thereby favoring the SAA structure. These major results from DFT calculations serve as a guide for experimentalists to explore new SAA catalysts. Further analysis has shown that SAAs have a unique electronic structure with a very sharp d-band feature close to the Fermi level, analogous to the electronic structure of molecular entities. This is one of the reasons that SAAs are particularly sought after: although they are metallic nanoparticles, they have properties akin to those of homogeneous catalysts. In this context, we have contributed extensive screening studies, focusing on molecular fragments of catalytic relevance on a range of SAAs, which have driven the identification of new catalysts. We have also explored the rich chemistry of two-adsorbate systems via kinetic modeling, demonstrating how a spectator species with greater affinity for the dopant can modulate the reactivity of the catalyst via the so-called (punctured) molecular cork effect.Since the first experimental characterization of SAAs about a decade ago, theoretical models have been able to support and explain various experimental observations. These models have served as benchmarks for assessing the predictive capability of the underlying theoretical methods. In turn, the predictions that have been delivered have guided and continue to guide the experimental research efforts in the field. These advancements show that the in silico design of new SAA catalysts is now within reach.

Putting Anion-π Interactions at Work for Catalysis.

Since its discovery two decades ago, anion-π interaction has been increasingly recognized as an important driving force. Extensive theoretical and experimental efforts on the ground-state anion-π binding and recognition have laid the bases for exploring its relevance in catalysis. Accordingly, the concept of "anion-π catalysis" that employing an electron-deficient π surface (π-acidic surface) for anionic reaction intermediate and transition state stabilization has emerged. This article shortly reviews the emergence and development of this concept, aiming to provide an emphasis on the general concept and key progress in this exciting area. To highlight the essential contribution of anion-π interactions, the contents are organized according to their role engaged in catalytic process, for example from both ground-state and transition-state stabilization to solely transition-state stabilization, mainly by a single π-face, and to cooperative π-face activation. A concluding remark and outlook on future development of this field is also given.

Material Science for catalysis: Quo vadis?

Material Science for catalysis: Quo vadis?

Plasma-Induced Heating Effects on Platinum Nanoparticle Size During Sputter Deposition Synthesis in Polymer and Ionic Liquid Substrates

Nanoparticle catalyst materials are becoming ever more important in a sustainable future. Specifically, platinum (Pt) nanoparticles have relevance in catalysis, in particular, fuel cell technologies. Sputter deposition into liquid substrates has been shown to produce nanoparticles without the presence of air and other contaminants and the need for precursors. Here, we produce Pt nanoparticles in three imidazolium-based ionic liquids and PEG 600. All Pt nanoparticles are crystalline and around 2 nm in diameter. We show that while temperature has an effect on particle size for Pt, it is not as great as for other materials. Sputtering power, time, and postheat treatment all show slight influence on the particle size, indicating the importance of temperature during sputtering. The temperature of the liquid substrate is measured and reaches over 150 °C during deposition which is found to increase the particle size by less than 20%, which is small compared to the effect of temperature on Au nanoparticles presented in the literature. High temperatures during Pt sputtering are beneficial for increasing Pt nanoparticle size beyond 2 nm. Better temperature control would allow for more control over the particle size in the future.

Paramagnetic NMR Spectroscopy of a Tri-Nuclear Copper Center from a Multicopper Oxidase, Laccase

Among metalloproteins multicopper oxidases and especially laccases are noteworthy because of their wide application in the fields of green chemistry, medicine, bioremediation and enzymatic biofuel cells. Laccases have a type 1 (T1) copper site for oxidation of substrates and a tri-nuclear copper center (TNC) for oxygen reduction reaction. The TNC comprises a binuclear type 3 (T3) site and a mononuclear type 2 (T2) site. We report the paramagnetic NMR spectra of a laccase from Streptomyces coelicolor, in which the Fermi-contact shifted (FCS) resonances were assigned to the coordinating histidine Nδ1/Hδ1 nuclei using tailored 1H-1H EXSY and 1H-15N HMQC experiments. The pNMR spectra of the resting oxidized state and the native intermediate state are shown. The FCS resonances from the NI state display two-state chemical exchange with exchange rates in the order of 100 s−1. This is supported by the observation of two different gz values from the EPR spectra. It is proposed that the exchange processes reflect rotational motion of histidine imidazole rings that coordinate the coppers in the TNC. To our knowledge this is the first report that shows multidimensional paramagnetic NMR spectra of the tri-nuclear copper center and the presence of chemical exchange in the tri-nuclear copper centre of a laccase. The potential catalytic relevance is under study.

Characterisation and reactivity of oxygen species at the surface of metal oxides

Surface reactive oxygen species play a fundamental role in selective oxidation and combustion reactions catalyzed by metal oxides. Unravelling the nature of these transient species, and understanding the details of both their electronic structure and reactivity has been for decades one of the prime research areas of surface and catalytic chemistry. The longstanding activity of Michel Che in this area has been a source of inspiration for generation of researchers, and constitute his outstanding and enduring scientific legacy. Present review provides a survey of the surface oxygen species on oxide materials, which moving on from the Che’s pioneering works includes noteworthy results obtained during the years by other researchers. In particular, applications of two powerful techniques such as electron paramagnetic resonance (EPR) and photoluminescence (PL) for detailed characterization of paramagnetic (O−, O2−, O3−) and diamagnetic surface oxygen varieties (O2−surf), respectively, are addressed here. Classification and insights into the formation pathways of these species on various oxide surfaces, as well as their involvement in model and real gas/solid and liquid/solid reactions of catalytic and photocatalytic relevance is also considered. Finally, the relationship between the thermodynamic and kinetic Bronsted basicity of low coordinated O2−Lc anions is discussed, on the basis of Che’s fundamental studies and on recent developments.

Antibody Probes of Module 1 of the 6-Deoxyerythronolide B Synthase Reveal an Extended Conformation During Ketoreduction.

The 6-deoxyerythronolide B synthase (DEBS) is a prototypical assembly line polyketide synthase (PKS) that synthesizes the macrocyclic core of the antibiotic erythromycin. Each of its six multidomain modules presumably sample distinct conformations, as biosynthetic intermediates tethered to their acyl carrier proteins interact with multiple active sites during the courses of their catalytic cycles. The spatiotemporal details underlying these protein dynamics remain elusive. Here, we investigate one aspect of this conformational flexibility using two domain-specific monoclonal antibody fragments (Fabs) isolated from a very large naïve human antibody library. Both Fabs, designated 1D10 and 2G10, were bound specifically and with high affinity to the ketoreductase domain of DEBS module 1 (KR1). Comparative kinetic analysis of stand-alone KR1 as well as a truncated bimodular derivative of DEBS revealed that 1D10 inhibited KR1 activity whereas 2G10 did not. Co-crystal structures of each KR1-Fab complex provided a mechanistic rationale for this difference. A hybrid PKS module harboring KR1 was engineered, whose individual catalytic domains have been crystallographically characterized at high resolution. Size exclusion chromatography coupled to small-angle X-ray scattering (SEC-SAXS) of this hybrid module bound to 1D10 provided further support for the catalytic relevance of the "extended" model of a PKS module. Our findings reinforce the power of monoclonal antibodies as tools to interrogate structure-function relationships of assembly line PKSs.