Metal-Ligand Cooperation with Thiols as Transient Cooperative Ligands: Acceleration and Inhibition Effects in (De)Hydrogenation Reactions.

ConspectusOver the past two decades, we have developed a series of pincer-type transition metal complexes capable of activating strong covalent bonds through a mode of reactivity known as metal-ligand cooperation (MLC). In such systems, an incoming substrate molecule simultaneously interacts with both the metal center and ligand backbone, with one part of the molecule reacting at the metal center and another part at the ligand. The majority of these complexes feature pincer ligands with a pyridine core, and undergo MLC through reversible dearomatization/aromatization of this pyridine moiety. This MLC platform has enabled us to perform a variety of catalytic dehydrogenation, hydrogenation, and related reactions, with high efficiency and selectivity under relatively mild conditions.In a typical catalytic complex that operates through MLC, the cooperative ligand remains coordinated to the metal center throughout the entire catalytic process, and this complex is the only catalytic species involved in the reaction. As part of our ongoing efforts to develop new catalytic systems featuring MLC, we have recently introduced the concept of transient cooperative ligand (TCL), i.e., a ligand that is capable of MLC when coordinated to a metal center, but the coordination of which is reversible rather than permanent. We have thus far employed thiol(ate)s as TCLs, in conjunction with an acridanide-based ruthenium(II)-pincer catalyst, and this has resulted in remarkable acceleration and inhibition effects in various hydrogenation and dehydrogenation reactions. A cooperative thiol(ate) ligand can be installed in situ by the simple addition of an appropriate thiol in an amount equivalent to the catalyst, and this has been repeatedly shown to enable efficient bond activation by MLC without the need for other additives, such as base. The use of an ancillary thiol ligand that is not fixed to the pincer backbone allows the catalytic system to benefit from a high degree of tunability, easily implemented by varying the added thiol. Importantly, thiols are coordinatively labile enough under typical catalytic conditions to leave a meaningful portion of the catalyst in its original unsaturated form, thereby allowing it to carry out its own characteristic catalytic activity. This generates two coexisting catalyst populations─one that contains a thiol(ate) ligand and another that does not─and this may lead to different catalytic outcomes, namely, enhancement of the original catalytic activity, inhibition of this activity, or the occurrence of diverging reactivities within the same catalytic reaction mixture. These thiol effects have enabled us to achieve a series of unique transformations, such as thiol-accelerated base-free aqueous methanol reforming, controlled stereodivergent semihydrogenation of alkynes using thiol as a reversible catalyst inhibitor, and hydrogenative perdeuteration of C═C bonds without using D2, enabled by a combination of thiol-induced acceleration and inhibition. We have also successfully realized the unprecedented formation of thioesters through dehydrogenative coupling of alcohols and thiols, as well as the hydrogenation of organosulfur compounds, wherein the cooperative thiol serves as a reactant or product. In this Account, we present an overview of the TCL concept and its various applications using thiols.

Polyoxymethylene Upcycling into Methanol and Methyl Groups Catalyzed by a Manganese Pincer Complex.

Polyoxymethylene (POM) is a commonly used engineering thermoplastic, but its recycling by conventional means, i.e., mechanical recycling, is not practiced to any meaningful extent, due to technical limitations. Instead, waste POM is typically incinerated or disposed in landfills, where it becomes a persistent environmental pollutant. An attractive alternative to mechanical recycling is upcycling, namely, the conversion of waste POM into value-added chemicals, but this has received very little attention. Herein, we report the upcycling of POM into useful chemicals through three different reactions, all of which are efficiently catalyzed by a single pincer complex of earth-abundant manganese. One method involves hydrogenation of POM into methanol using H2 gas as the only reagent, whereas another method converts POM into methanol and CO2 through a one-pot process comprising acidolysis followed by Mn-catalyzed disproportionation. The third method utilizes POM as a reagent for the methylation of ketones and amines.

Homogeneous Catalysis for Sustainable Energy: Hydrogen and Methanol Economies, Fuels from Biomass, and Related Topics.

As the world pledges to significantly cut carbon emissions, the demand for sustainable and clean energy has now become more important than ever. This includes both production and storage of energy carriers, a majority of which involve catalytic reactions. This article reviews recent developments of homogeneous catalysts in emerging applications of sustainable energy. The most important focus has been on hydrogen storage as several efficient homogeneous catalysts have been reported recently for (de)hydrogenative transformations promising to the hydrogen economy. Another direction that has been extensively covered in this review is that of the methanol economy. Homogeneous catalysts investigated for the production of methanol from CO2, CO, and HCOOH have been discussed in detail. Moreover, catalytic processes for the production of conventional fuels (higher alkanes such as diesel, wax) from biomass or lower alkanes have also been discussed. A section has also been dedicated to the production of ethylene glycol from CO and H2 using homogeneous catalysts. Well-defined transition metal complexes, in particular, pincer complexes, have been discussed in more detail due to their high activity and well-studied mechanisms.

Calcium-Ligand Cooperation Promoted Activation of N2O, Amine, and H2 as well as Catalytic Hydrogenation of Imines, Quinoline, and Alkenes.

Bond activation and catalysis using s-block metals are of great significance. Herein, a series of calcium pincer complexes with deprotonated side arms have been prepared using pyridine-based PNP and PNN ligands. The complexes were characterized by NMR and X-ray crystal diffraction. Utilizing the obtained calcium complexes, unprecedented N2O activation by metal-ligand cooperation (MLC) involving dearomatization-aromatization of the pyridine ligand was achieved, generating aromatized calcium diazotate complexes as products. Additionally, the dearomatized calcium complexes were able to activate the N-H bond as well as reversibly activate H2, offering an opportunity for the catalytic hydrogenation of various unsaturated molecules. DFT calculations were applied to analyze the electronic structures of the synthesized complexes and explore possible reaction mechanisms. This study is an important complement to the area of MLC and main-group metal chemistry.

Designing New Magnesium Pincer Complexes for Catalytic Hydrogenation of Imines and N-Heteroarenes: H2 and N-H Activation by Metal-Ligand Cooperation as Key Steps.

Utilization of main-group metals as alternatives to transition metals in homogeneous catalysis has become a hot research area in recent years. However, their application in catalytic hydrogenation is less common due to the difficulty in heterolytic cleavage of the H-H bond. Employing aromatization/de-aromatization metal-ligand cooperation (MLC) highly enhances the H2 activation process, offering an efficient approach for the hydrogenation of unsaturated molecules catalyzed by main-group metals. Herein, we report a series of new magnesium pincer complexes prepared using PNNH-type pincer ligands. The complexes were characterized by NMR and X-ray single-crystal diffraction. Reversible activation of H2 and N-H bonds by MLC employing these pincer complexes was developed. Using the new magnesium complexes, homogeneously catalyzed hydrogenation of aldimines and ketimines was achieved, affording secondary amines in excellent yields. Control experiments and DFT studies reveal that a pathway involving MLC is favorable for the hydrogenation reactions. Moreover, the efficient catalysis was extended to the selective hydrogenation of quinolines and other N-heteroarenes, presenting the first example of hydrogenation of N-heteroarenes homogeneously catalyzed by early main-group metal complexes. This study provides a new strategy for hydrogenation of C═N bonds catalyzed by magnesium compounds and enriches the research of main-group metal catalysis.

Oxidation of Organic Compounds Using Water as the Oxidant with H2 Liberation Catalyzed by Molecular Metal Complexes.

Oxidation reactions of organic compounds play a central role in both industrial chemical and material synthesis as well as in fine chemical and pharmaceutical synthesis. While traditional laboratory-scale oxidative syntheses have relied on the use of strong oxidizers, modern large-scale oxidation processes preferentially utilize air or pure O2 as an oxidant, with other oxidants such as hydrogen peroxide, nitric acid, and aqueous chlorine solution also being used in some processes. The use of molecular oxygen or air as an oxidant has been very attractive in recent decades because of the abundance of air and the lack of wasteful byproduct generation. Nevertheless, the use of high-pressure air or, in particular, pure oxygen can lead to serious safety concerns with improper handling and also necessitates the use of sophisticated high-pressure reactors for the processes.Several research groups, including ours, have investigated in recent times the possibility of carrying out catalytic oxidation reactions using water as the formal oxidant, with no added conventional oxidants. Along with the abundant availability of water, these processes also generate dihydrogen gas as the reaction coproduct, which is a highly valuable fuel. Several well-defined molecular metal complexes have been reported in recent years to catalyze these unusual oxidative reactions with water. A ruthenium bipyridine-based PNN pincer complex was reported by us to catalyze the oxidation of primary alcohols to carboxylate salts with alkaline water along with H2 liberation, followed by reports by other groups using other complexes as catalysts. At the same time, ruthenium-, iridium-, and rhodium-based complexes have been reported to catalyze aldehyde oxidation to carboxylic acids using water. Our group has combined the catalytic aqueous alcohol and aldehyde oxidation activity of a ruthenium complex to achieve the oxidation of biomass-derived renewable aldehydes such as furfural and 5-hydroxymethylfurfural (HMF) to furoic acid and furandicarboxylic acid (FDCA), respectively, using alkaline water as the oxidant, liberating H2. Ruthenium complexes with an acridine-based PNP ligand have also been employed by our group for the catalytic oxidation of amines to the corresponding lactams, or to carboxylic acids via a deaminative route, using water. Similarly, we also reported molecular complexes for the catalytic Markovnikov oxidation of alkenes to ketones using water, similar to Wacker-type oxidation, which, however, does not require any terminal oxidant and produces H2 as the coproduct. At the same time, the oxidation of enol ethers to the corresponding esters with water has also been reported. This account will highlight these recent advances where water was used as an oxidant to carry out selective oxidation reactions of organic compounds, catalyzed by well-defined molecular complexes, with H2 liberation. The oxidation of alcohols, aldehydes, amines, alkenes, and enol ethers will be discussed to provide an outlook toward other functional groups' oxidation. We hope that this will aid researchers in devising other oxidative dehydrogenative catalytic systems using water, complementing traditional oxidative processes involving strong oxidants and molecular oxygen.

Catalytic Furfural/5-Hydroxymethyl Furfural Oxidation to Furoic Acid/Furan-2,5-dicarboxylic Acid with H2 Production Using Alkaline Water as the Formal Oxidant.

Furfural and 5-hydroxymethyl furfural (HMF) are abundantly available biomass-derived renewable chemical feedstocks, and their oxidation to furoic acid and furan-2,5-dicarboxylic acid (FDCA), respectively, is a research area with huge prospective applications in food, cosmetics, optics, and renewable polymer industries. Water-based oxidation of furfural/HMF is a lucrative approach for simultaneous generation of H2 and furoic acid/FDCA. However, this process is currently limited to (photo)electrochemical methods that can be challenging to control, improve, and scale up. Herein, we report well-defined ruthenium pincer catalysts for direct homogeneous oxidation of furfural/HMF to furoic acid/FDCA, using alkaline water as the formal oxidant while producing pure H2 as the reaction byproduct. Mechanistic studies indicate that the ruthenium complex not only catalyzes the aqueous oxidation but also actively suppresses background decomposition by facilitating initial Tishchenko coupling of substrates, which is crucial for reaction selectivity. With further improvement, this process can be used in scaled-up facilities for a simultaneous renewable building block and fuel production.

Controlled Selectivity through Reversible Inhibition of the Catalyst: Stereodivergent Semihydrogenation of Alkynes.

Catalytic semihydrogenation of internal alkynes using H2 is an attractive atom-economical route to various alkenes, and its stereocontrol has received widespread attention, both in homogeneous and heterogeneous catalyses. Herein, a novel strategy is introduced, whereby a poisoning catalytic thiol is employed as a reversible inhibitor of a ruthenium catalyst, resulting in a controllable H2-based semihydrogenation of internal alkynes. Both (E)- and (Z)-alkenes were obtained efficiently and highly selectively, under very mild conditions, using a single homogeneous acridine-based ruthenium pincer catalyst. Mechanistic studies indicate that the (Z)-alkene is the reaction intermediate leading to the (E)-alkene and that the addition of a catalytic amount of bidentate thiol impedes the Z/E isomerization step by forming stable ruthenium thiol(ate) complexes, while still allowing the main hydrogenation reaction to proceed. Thus, the absence or presence of catalytic thiol controls the stereoselectivity of this alkyne semihydrogenation, affording either the (E)-isomer as the final product or halting the reaction at the (Z)-intermediate. The developed system, which is also applied to the controllable isomerization of a terminal alkene, demonstrates how metal catalysis with switchable selectivity can be achieved by reversible inhibition of the catalyst with a simple auxiliary additive.

Magnesium Pincer Complexes and Their Applications in Catalytic Semihydrogenation of Alkynes and Hydrogenation of Alkenes: Evidence for Metal-Ligand Cooperation.

The development of catalysts for environmentally benign organic transformations is a very active area of research. Most of the catalysts reported so far are based on transition-metal complexes. In recent years, examples of catalysis by main-group metal compounds have been reported. Herein, we report a series of magnesium pincer complexes, which were characterized by NMR and X-ray single-crystal diffraction. Reversible activation of H2 via aromatization/dearomatization metal-ligand cooperation was studied. Utilizing the obtained complexes, the unprecedented homogeneous main-group metal catalyzed semihydrogenation of alkynes and hydrogenation of alkenes were demonstrated under base-free conditions, affording Z-alkenes and alkanes as products, respectively, with excellent yields and selectivities. Control experiments and DFT studies reveal the involvement of metal-ligand cooperation in the hydrogenation reactions. This study not only provides a new approach for the semihydrogenation of alkynes and hydrogenation of alkenes catalyzed by magnesium but also offers opportunities for the hydrogenation of other compounds catalyzed by main-group metal complexes.

Efficient Base-Free Aqueous Reforming of Methanol Homogeneously Catalyzed by Ruthenium Exhibiting a Remarkable Acceleration by Added Catalytic Thiol.

Production of H2 by methanol reforming is of particular interest due the low cost, ready availability, and high hydrogen content of methanol. However, most current methods either require very high temperatures and pressures or strongly rely on the utilization of large amounts of base. Here we report an efficient, base-free aqueous-phase reforming of methanol homogeneously catalyzed by an acridine-based ruthenium pincer complex, the activity of which was unexpectedly improved by a catalytic amount of a thiol additive. The reactivity of this system is enhanced by nearly 2 orders of magnitude upon addition of the thiol, and it can maintain activity for over 3 weeks, achieving a total H2 turnover number of over 130 000. On the basis of both experimental and computational studies, a mechanism is proposed which involves outer-sphere dehydrogenations promoted by a unique ruthenium complex with thiolate as an assisting ligand. The current system overcomes the need for added base in homogeneous methanol reforming and also highlights the unprecedented acceleration of catalytic activity of metal complexes achieved by the addition of a catalytic amount of thiol.

Homogeneous Reforming of Aqueous Ethylene Glycol to Glycolic Acid and Pure Hydrogen Catalyzed by Pincer-Ruthenium Complexes Capable of Metal-Ligand Cooperation.

Glycolic acid is a useful and important α-hydroxy acid that has broad applications. Herein, the homogeneous ruthenium catalyzed reforming of aqueous ethylene glycol to generate glycolic acid as well as pure hydrogen gas, without concomitant CO2 emission, is reported. This approach provides a clean and sustainable direction to glycolic acid and hydrogen, based on inexpensive, readily available, and renewable ethylene glycol using 0.5 mol % of catalyst. In-depth mechanistic experimental and computational studies highlight key aspects of the PNNH-ligand framework involved in this transformation.

Oxidation of Alkenes by Water with H2 Liberation.

Oxidation by water with H2 liberation is highly desirable, as it can serve as an environmentally friendly way for the oxidation of organic compounds. Herein, we report the oxidation of alkenes with water as the oxidant by using a catalyst combination of a dearomatized acridine-based PNP-Ru complex and indium(III) triflate. Compared to traditional Wacker-type oxidation, this transformation avoids the use of added chemical oxidants and liberates hydrogen gas as the only byproduct.

Catalytic Hydrogenation of Thioesters, Thiocarbamates, and Thioamides.

Direct hydrogenation of thioesters with H2 provides a facile and waste-free method to access alcohols and thiols. However, no report of this reaction is documented, possibly because of the incompatibility of the generated thiol with typical hydrogenation catalysts. Here, we report an efficient and selective hydrogenation of thioesters. The reaction is catalyzed by an acridine-based ruthenium complex without additives. Various thioesters were fully hydrogenated to the corresponding alcohols and thiols with excellent tolerance for amide, ester, and carboxylic acid groups. Thiocarbamates and thioamides also undergo hydrogenation under similar conditions, substantially extending the application of hydrogenation of organosulfur compounds.

Metal-Ligand Cooperation Facilitates Bond Activation and Catalytic Hydrogenation with Zinc Pincer Complexes.

A series of PNP zinc pincer complexes capable of bond activation via aromatization/dearomatization metal-ligand cooperation (MLC) were prepared and characterized. Reversible heterolytic N-H and H-H bond activation by MLC is shown, in which hemilability of the phosphorus linkers plays a key role. Utilizing this zinc pincer system, base-free catalytic hydrogenation of imines and ketones is demonstrated. A detailed mechanistic study supported by computation implicates the key role of MLC in facilitating effective catalysis. This approach offers a new strategy for (de)hydrogenation and other catalytic transformations mediated by zinc and other main group metals.

Catalytic Oxidative Deamination by Water with H2 Liberation.

Selective oxidative deamination has long been considered to be an important but challenging transformation, although it is a common critical process in the metabolism of bioactive amino compounds. Most of the synthetic methods developed so far rely on the use of stoichiometric amounts of strong and toxic oxidants. Here we present a green and efficient method for oxidative deamination, using water as the oxidant, catalyzed by a ruthenium pincer complex. This unprecedented reaction protocol liberates hydrogen gas and avoids the use of sacrificial oxidants. A wide variety of primary amines are selectively transformed to carboxylates or ketones in good to high yields. It is noteworthy that mechanistic experiments and DFT calculations indicate that in addition to serving as the oxidant, water also plays an important role in assisting the hydrogen liberation steps involved in amine dehydrogenation.

Hydrogenative Depolymerization of Nylons.

The widespread crisis of plastic pollution demands discovery of new and sustainable approaches to degrade robust plastics such as nylons. Using a green and sustainable approach based on hydrogenation, in the presence of a ruthenium pincer catalyst at 150 °C and 70 bar H2, we report here the first example of hydrogenative depolymerization of conventional, widely used nylons and polyamides, in general. Under the same catalytic conditions, we also demonstrate the hydrogenation of a polyurethane to produce diol, diamine, and methanol. Additionally, we demonstrate an example where monomers (and oligomers) obtained from the hydrogenation process can be dehydrogenated back to a poly(oligo)amide of approximately similar molecular weight, thus completing a closed loop cycle for recycling of polyamides. Based on the experimental and density functional theory studies, we propose a catalytic cycle for the process that is facilitated by metal-ligand cooperativity. Overall, this unprecedented transformation, albeit at the proof of concept level, offers a new approach toward a cleaner route to recycling nylons.

A Reversible Liquid-to-Liquid Organic Hydrogen Carrier System Based on Ethylene Glycol and Ethanol.

Liquid organic hydrogen carriers (LOHCs) are powerful systems for the efficient unloading and loading molecular hydrogen. Herein, a liquid-to-liquid organic hydrogen carrier system based on reversible dehydrogenative coupling of ethylene glycol (EG) with ethanol catalysed by ruthenium pincer complexes is reported. Noticeable advantages of the current LOHC system is that both reactants (hydrogen-rich components) and the produced esters (hydrogen-lean components) are liquids at room temperature, and the dehydrogenation process can be performed under solvent and base-free conditions. Moreover, the hydrogenation reaction proceeds under low hydrogen pressure (5 bar), and the LOHC system has a relatively high theoretical gravimetric hydrogen storage capacity (HSC>5.0 wt %), presenting an attractive hydrogen storage system.

Synthesis and Reactivity of Cationic Boron Complexes Distorted by Pyridine-based Pincer Ligands: Isolation of a Photochemical Hofmann-Martius-type Intermediate.

A family of cationic boron complexes was synthesized, using a dianilidopyridine pincer ligand, which imposes in-plane distortion of the geometry at boron towards T-shaped. Reactivity of these cations toward hydride and base was investigated, and the utility of these cations as precursors to a variety of π-conjugated BN heterocycles was demonstrated. 300 nm irradiation of a deprotonated pincer boron complex triggered a C-N cleavage/C-C formation yielding a dearomatized boryl imine, which has a structure akin to the long-proposed intermediate in the photochemical Hofmann-Martius rearrangement. The photo-rearrangement triggers relief of the distortion imposed by the pincer ligand.

Mechanism of the Manganese-Pincer-Catalyzed Acceptorless Dehydrogenative Coupling of Nitriles and Alcohols.

A recent study showed that a Mn-pincer could catalyze the acceptorless dehydrogenative coupling of nitriles and alcohols to yield acrylonitriles. The reaction mechanism proposed in that work contained some intermediates that, in most of the cases, were not characterized. Moreover, one of the intermediates involved a charged separation, which is unlikely in apolar solvents. To clarify the reaction mechanism of this critical reaction, we decided to perform a DFT study. Our results prove the existence of a cooperative effect of the metal and the ligand in several steps of the catalytic cycle. We also find the presence of several equilibria between isomeric intermediates where water, or the same alcohol reagent, takes part in assisting the proton transfer. Furthermore, we have analyzed the charge-separated structure proposed experimentally and have found a nearly pure covalent bond between the two expected charged moieties. Finally, the Knoevenagel condensation step that generates the acrylonitrile is found to be the rate-determining step.

Formamides as Isocyanate Surrogates: A Mechanistically Driven Approach to the Development of Atom-Efficient, Selective Catalytic Syntheses of Ureas, Carbamates, and Heterocycles.

Despite the hazardous nature of isocyanates, they remain key building blocks in bulk and fine chemical synthesis. By surrogating them with less potent and readily available formamide precursors, we herein demonstrate an alternative, mechanistic approach to selectively access a broad range of ureas, carbamates, and heterocycles via ruthenium-based pincer complex catalyzed acceptorless dehydrogenative coupling reactions. The design of these highly atom-efficient procedures was driven by the identification and characterization of the relevant organometallic complexes, uniquely exhibiting the trapping of an isocyanate intermediate. Density functional theory (DFT) calculations further contributed to shed light on the remarkably orchestrated chain of catalytic events, involving metal-ligand cooperation.