Synthesis, Characterization, and Catalytic Application of Colloidal and Supported Manganese Nanoparticles.

Colloidal and supported manganese nanoparticles were synthesized following an organometallic approach and applied in the catalytic transfer hydrogenation (CTH) of aldehydes and ketones. Reaction parameters for the preparation of colloidal nanoparticles (NPs) were optimized to yield small (2-2.5 nm) and well-dispersed NPs. Manganese NPs were further immobilized on an imidazolium-based supported ionic phase (SILP) and characterized to evaluate NP size, metal loading, and oxidation states. Oxidation of the Mn NPs by the support was observed resulting in an average formal oxidation state of +2.5. The MnOx@SILP material showed promising performance in the CTH of aldehydes and ketones using 2-propanol as a hydrogen donor, outperforming previously reported Mn NPs-based CTH catalysts in terms of metal loading-normalized turnover numbers. Interestingly, MnOx@SILP were found to lose activity upon air exposure, which correlates with an additional increase in the average oxidation state of Mn as revealed by X-ray absorption spectroscopic studies.

A Cooperative Cobalt-Driven System for One-Carbon Extension in the Synthesis of (Z)-Silyl Enol Ethers from Aldehydes: Unlocking Regio- and Stereoselectivity.

The research presented herein explores a cobalt-based catalytic system, distinctively featuring a cooperative boron-centric element within its intricate ligand architecture. This system is strategically engineered to enable the integration of a singular carbon atom into aldehydes, a process culminating in the production of (Z)-silyl enol ethers. Beyond offering an efficient one-pot synthesis route, this method adeptly overcomes challenges inherent to conventional techniques, such as the need for large amounts of additives, restrictive functional group tolerance, and extreme reaction temperatures. Initial mechanistic studies suggest the potential role of a cobalt-carbene complex as a catalytically significant species and underscore the importance of the borane segment. Collectively, these observations highlight the potential of this system in advancing complex bond activation pursuits.

A Cooperative Rhodium/Secondary Phosphine Oxide [Rh/P(O)nBu2 ] Template for Catalytic Hydrodefluorination of Perfluoroarenes.

The selective activation of C-F bonds under mild reaction conditions remains an ongoing challenge of bond activation. Here, we present a cooperative [Rh/P(O)nBu2 ] template for catalytic hydrodefluorination (HDF) of perfluoroarenes. In addition to substrates presenting electron-withdrawing functional groups, the system showed an exceedingly rare tolerance for electron-donating functionalities and heterocycles. The high chemoselectivity of the catalyst and its readiness to be deployed at a preparative scale illustrate its practicality. Empirical mechanistic studies and a density functional theory (DFT) study have identified a rhodium(I) dihydride complex as a catalytically relevant species and the determining role of phosphine oxide as a cooperative fragment. Altogether, we demonstrate that molecular templates based on these design elements can be assembled to create catalysts with increased reactivity for challenging bond activations.

Theory-guided development of homogeneous catalysts for the reduction of CO2 to formate, formaldehyde, and methanol derivatives.

The stepwise catalytic reduction of carbon dioxide (CO2) to formic acid, formaldehyde, and methanol opens non-fossil pathways to important platform chemicals. The present article aims at identifying molecular control parameters to steer the selectivity to the three distinct reduction levels using organometallic catalysts of earth-abundant first-row metals. A linear scaling relationship was developed to map the intrinsic reactivity of 3d transition metal pincer complexes to their activity and selectivity in CO2 hydrosilylation. The hydride affinity of the catalysts was used as a descriptor to predict activity/selectivity trends in a composite volcano picture, and the outstanding properties of cobalt complexes bearing bis(phosphino)triazine PNP-type pincer ligands to reach the three reduction levels selectively under different reaction conditions could thus be rationalized. The implications of the composite volcano picture were successfully experimentally validated with selected catalysts, and the challenging intermediate level of formaldehyde could be accessed in over 80% yield with the cobalt complex 6. The results underpin the potential of tandem computational-experimental approaches to propel catalyst design for CO2-based chemical transformations.

An Adaptive Rhodium Catalyst to Control the Hydrogenation Network of Nitroarenes.

An adaptive catalytic system that provides control over the nitroarene hydrogenation network to prepare a wide range of aniline and hydroxylamine derivatives is presented. This system takes advantage of a delicate interplay between a rhodium(III) center and a Lewis acidic borane introduced in the secondary coordination sphere of the metal. The high chemoselectivity of the catalyst in the presence of various potentially vulnerable functional groups and its readiness to be deployed at a preparative scale illustrate its practicality. Mechanistic studies and density functional theory (DFT) methods were used to shed light on the mode of functioning of the catalyst and elucidate the origin of adaptivity. The competition for interaction with boron between a solvent molecule and a substrate was found crucial for adaptivity. When operating in THF, the reduction network stops at the hydroxylamine platform, whereas the reaction can be directed to the aniline platform in toluene.

Selective oxidation of silanes into silanols with water using [MnBr(CO)5] as a precatalyst.

The development of earth-abundant catalysts for the selective conversion of silanes to silanols with water as an oxidant generating valuable hydrogen as the only by-product continues to be a challenge. Here, we demonstrate that [MnBr(CO)5] is a highly active precatalyst for this reaction, operating under neutral conditions and avoiding the undesired formation of siloxanes. As a result, a broad substrate scope, including primary and secondary silanes, could be converted to the desired products. The turnover performances of the catalyst were also examined, yielding a maximum TOF of 4088 h-1. New light was shed on the debated mechanism of the interaction between [MnBr(CO)5] and Si-H bonds based on the reaction kinetics (including KIEs of PhMe2SiD and D2O) and spectroscopic techniques (FT-IR, GC-TCD, 1H-, 29Si-, and 13C-NMR). The initial activation of [MnBr(CO)5] was found to result from the formation of a manganese(i) hydride species and R3SiBr, and the experimental data are most consistent with a catalytic cycle comprising a cationic tricarbonyl Mn(i) unit as the active framework.

Cobalt-Catalyzed Hydrosilylation of Carbon Dioxide to the Formic Acid, Formaldehyde, and Methanol Level-How to Control the Catalytic Network?

The selective hydrosilylation of carbon dioxide (CO2) to either the formic acid, formaldehyde, or methanol level using a molecular cobalt(II) triazine complex can be controlled based on reaction parameters such as temperature, CO2 pressure, and concentration. Here, we rationalize the catalytic mechanism that enables the selective arrival at each product platform. Key reactive intermediates were prepared and spectroscopically characterized, while the catalytic mechanism and the energy profile were analyzed with density functional theory (DFT) methods and microkinetic modeling. It transpired that the stepwise reduction of CO2 involves three consecutive catalytic cycles, including the same cobalt(I) triazine hydride complex as the active species. The increasing kinetic barriers associated with each reduction step and the competing hydride transfer steps in the three cycles corroborate the strong influence of the catalyst environment on the product selectivity. The fundamental mechanistic insights provide a consistent description of the catalytic system and rationalize, in particular, the experimentally verified opportunity to steer the reaction toward the formaldehyde product as the chemically most challenging reduction level.

Systematic Variation of 3d Metal Centers in a Redox-Innocent Ligand Environment: Structures, Electrochemical Properties, and Carbon Dioxide Activation.

Coordination compounds of earth-abundant 3d transition metals are among the most effective catalysts for the electrochemical reduction of carbon dioxide (CO2). While the properties of the metal center are crucial for the ability of the complexes to electrochemically activate CO2, systematic variations of the metal within an identical, redox-innocent ligand backbone remain insufficiently investigated. Here, we report on the synthesis, structural and spectroscopic characterization, and electrochemical investigation of a series of 3d transition-metal complexes [M = Mn(I), Fe(II), Co(II), Ni(II), Cu(I), and Zn(II)] coordinated by a new redox-innocent PNP pincer ligand system. Only the Fe, Co, and Ni complexes reveal distinct metal-centered electrochemical reductions from M(II) down to M(0) and show indications for interaction with CO2 in their reduced states. The Ni(0) d10 species associates with CO2 to form a putative Aresta-type Ni-η2-CO2 complex, where electron transfer to CO2 through back-bonding is insufficient to enable electrocatalytic activity. By contrast, the Co(0) d9 intermediate binding CO2 can undergo additional electron uptake into a formal cobalt(I) metallacarboxylate complex able to promote turnover. Our data, together with the few literature precedents, single out that an unsaturated coordination sphere (coordination number = 4 or 5) and a d7-to-d9 configuration in the reduced low oxidation state (+I or 0) are characteristics that foster electrochemical CO2 activation for complexes based on redox-innocent ligands.

Acceptorless Dehydrogenation of Methanol to Carbon Monoxide and Hydrogen using Molecular Catalysts.

The acceptorless dehydrogenation of methanol to carbon monoxide and hydrogen was investigated using homogeneous molecular complexes. Complexes of ruthenium and manganese comprising the MACHO ligand framework showed promising activities for this reaction. The molecular ruthenium complex [RuH(CO)(BH4 )(HN(C2 H4 PPh2 )2 )] (Ru-MACHO-BH) achieved up to 3150 turnovers for carbon monoxide and 9230 turnovers for hydrogen formation at 150 °C reaching pressures up to 12 bar when the decomposition was carried out in a closed vessel. Control experiments affirmed that the metal complex mediates the initial fast dehydrogenation of methanol to formaldehyde and methyl formate followed by subsequent slow decarbonylation. Depending on the catalyst and reaction conditions, the CO/H2 ratio in the gas mixture thus varies over a broad range from almost pure hydrogen to the stoichiometric limit of 1:2.

Alcohol-Assisted Hydrogenation of Carbon Monoxide to Methanol Using Molecular Manganese Catalysts.

Alcohol-assisted hydrogenation of carbon monoxide (CO) to methanol was achieved using homogeneous molecular complexes. The molecular manganese complex [Mn(CO)2Br[HN(C2H4P i Pr2)2]] ([HN(C2H4P i Pr2)2] = MACHO- i Pr) revealed the best performance, reaching up to turnover number = 4023 and turnover frequency 857 h-1 in EtOH/toluene as solvent under optimized conditions (T = 150 °C, p(CO/H2) = 5/50 bar, t = 8-12 h). Control experiments affirmed that the reaction proceeds via formate ester as the intermediate, whereby a catalytic amount of base was found to be sufficient to mediate its formation from CO and the alcohol in situ. Selectivity for methanol formation reached >99% with no accumulation of the formate ester. The reaction was demonstrated to work with methanol as the alcohol component, resulting in a reactive system that allows catalytic "breeding" of methanol without any coreagents.

Reduction of Carboxylic Acids to Alcohols via Manganese(I) Catalyzed Hydrosilylation.

The reduction of carboxylic acids to the respective alcohols, in mild conditions, was achieved using [MnBr(CO)5] as the catalyst and bench stable PhSiH3 as the reducing agent. It was shown that the reaction with the earth-abundant metal catalyst could be performed either with a catalyst loading as low as 0.5 mol %, rare with the use of [MnBr(CO)5], or on a gram scale employing only 1.5 equiv of PhSiH3, the lowest amount of silane reported to date for this transformation. Kinetic data and control experiments have provided initial insight into the mechanism of the catalytic process, suggesting that it proceeds via the formation of silyl ester intermediates and ligand dissociation to generate a coordinatively unsaturated Mn(I) complex as the active species.

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

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

Rhodium(i) complexes derived from tris(isopropyl)-azaphosphatrane-controlling the metal-ligand interplay.

Proazaphosphatranes are intriguing ligand architectures comprising a bicyclic cage of flexible nature. They can undergo structural deformations due to transannulation while displaying modular electronic and steric properties. Herein, we report the synthesis and coordination chemistry of rhodium(i) complexes bearing a tris(isopropyl)-azaphosphatrane (TiPrAP) ligand. The molecular structure of the primary complex (1) revealed the insertion of the metal center into a P-N bond of the ligand. The addition of a Lewis acid, i.e., lithium chloride, promoted the dynamic behavior of the complex in the solution, which was studied by state-of-the-art NMR spectroscopy. Substituting the cyclooctadiene ligand at the metal center with triphenylphosphine or 2-pyridyldiphenylphosphine unveiled the adaptive nature of the TiPrAP backbone capable of switching its axial nitrogen from interacting with the phosphorus atom to coordinate the rhodium center. This led the entire ligand edifice to change its binding to rhodium from a bidentate to tridentate coordination. Altogether, our study shows that introducing a TiPrAP ligand allows for unique molecular control of the immediate environment of the metal center, opening perspectives in controlled bond activation and catalysis.

Controlling the Product Platform of Carbon Dioxide Reduction: Adaptive Catalytic Hydrosilylation of CO2 Using a Molecular Cobalt(II) Triazine Complex.

The catalytic reduction of carbon dioxide (CO2 ) is considered a major pillar of future sustainable energy systems and chemical industries based on renewable energy and raw materials. Typically, catalysts and catalytic systems are transforming CO2 preferentially or even exclusively to one of the possible reduction levels and are then optimized for this specific product. Here, we report a cobalt-based catalytic system that enables the adaptive and highly selective transformation of carbon dioxide individually to either the formic acid, the formaldehyde, or the methanol level, demonstrating the possibility of molecular control over the desired product platform.

Hydroamination of Aromatic Alkynes to Imines Catalyzed by Pd(II)-Anthraphos Complexes.

Herein, we report the synthesis, characterization, and catalytic performance of cationic Pd(II)-Anthraphos complexes in the intermolecular hydroamination of aromatic alkynes with aromatic amines. The reaction proceeds with 0.18 mol % of catalyst loading, at 90 °C for 4 h under neat conditions. Good to excellent yields could be obtained for a broad range of amines and alkynes.

Conversion of a Fleeting Open-Shell Iron Nitride into an Iron Nitrosyl.

Terminal metal nitrides have been proposed as key intermediates in a series of pivotal chemical transformations. However, exploring the chemical activity of transient tetragonal iron(V) nitrides is largely impeded by their facile dimerization in fluid solutions. Herein, in situ EPR and Mössbauer investigations are presented of unprecedented oxygenation of a paramagnetic iron(V) nitrido intermediate, [FeV N(cyclam-ac)]+ (2, cyclam-ac- =1,4,8,11-tetraazacyclotetradecane-1-acetate anion), yielding an iron nitrosyl complex, [Fe(NO)(cyclam-ac)]+ (3). Further theoretical studies suggest that during the reaction a closed-shell singlet O atom is transferred to 2. Consequently, the N-O bond formation does not follow a radical coupling mechanism proposed for the N-N bond formation but is accomplished by three mutual electron-transfer pathways between 2 and the O atom donor, thanks to the ambiphilic nature of 2.

Systematic ligand variation to modulate the electrochemical properties of iron and manganese complexes.

A series of iron(+iii) and manganese(+ii) complexes based on the dpaqR-ligand system (dpaq = 2-[bis(pyridine-2-ylmethyl)]amino-N-quinolin-8-yl-acetamide) were investigated using cyclic voltammetry (CV) to elucidate how the electronic properties of the ligands influence the overpotential and catalytic current in the context of water oxidation catalysis. For the Fe-complexes an electron withdrawing NO2 or CF3 group attached to the 5-position of the quinoline unit increased the catalytic current, but only with a simultaneous increase of the overpotential. However, when a pyrene moiety was attached to the dipicolylamine unit of the ligand, the overpotential decreased with concomitant increase of the catalytic current. Although the manganese complexes showed no reversible formation of a molecular catalytically active species for water oxidation, the variations of the ligand scaffold affected largely the same trends in their electrochemical behavior.

Aminotriazole Mn(I) Complexes as Effective Catalysts for Transfer Hydrogenation of Ketones.

A catalytic system based on complexes comprising abundant and cheap manganese together with readily available aminotriazole ligands is reported. The new Mn(I) complexes are catalytically competent in transfer hydrogenation of ketones with 2-propanol as hydrogen source. The reaction proceeds under mild conditions at 80 °C for 20 h with 3 % of catalyst loading using either KO t Bu or NaOH as base. Good to excellent yields were obtained for a wide substrate scope with broad functional group tolerance. The obtained results by varying the substitution pattern of the ligand are consistent with an out-sphere mechanism for the H-transfer.

Manganese-catalyzed hydroboration of carbon dioxide and other challenging carbonyl groups.

Reductive functionalization of the C=O unit in carboxylic acids, carbonic acid derivatives, and ultimately in carbon dioxide itself is a challenging task of key importance for the synthesis of value-added chemicals. In particular, it can open novel pathways for the valorization of non-fossil feedstocks. Catalysts based on earth-abundant, cheap, and benign metals would greatly contribute to the development of sustainable synthetic processes derived from this concept. Herein, a manganese pincer complex [Mn(Ph2PCH2SiMe2)2NH(CO)2Br] (1) is reported to enable the reduction of a broad range of carboxylic acids, carbonates, and even CO2 using pinacolborane as reducing agent. The complex is shown to operate under mild reaction conditions (80-120 °C), low catalyst loadings (0.1-0.2 mol%) and runs under solvent-less conditions. Mechanistic studies including crystallographic characterisation of a borane adduct of the pincer complex (1) imply that metal-ligand cooperation facilitates substrate activation.

Structure and Reactivity of Half-Sandwich Rh(+3) and Ir(+3) Carbene Complexes. Catalytic Metathesis of Azobenzene Derivatives.

Traditional rhodium carbene chemistry relies on the controlled decomposition of diazo derivatives with [Rh2(OAc)4] or related dinuclear Rh(+2) complexes, whereas the use of other rhodium sources is much less developed. It is now shown that half-sandwich carbene species derived from [Cp*MX2]2 (M = Rh, Ir; X = Cl, Br, I, Cp* = pentamethylcyclopentadienyl) also exhibit favorable application profiles. Interestingly, the anionic ligand X proved to be a critical determinant of reactivity in the case of cyclopropanation, epoxide formation and the previously unknown catalytic metathesis of azobenzene derivatives, whereas the nature of X does not play any significant role in -OH insertion reactions. This perplexing disparity can be explained on the basis of spectral and crystallographic data of a representative set of carbene complexes of this type, which could be isolated despite their pronounced electrophilicity. Specifically, the donor/acceptor carbene 10a derived from ArC(═N2)COOMe and [Cp*RhCl2]2 undergoes spontaneous 1,2-migratory insertion of the emerging carbene unit into the Rh-Cl bond with formation of the C-metalated rhodium enolate 11. In contrast, the analogous complexes 10b,c derived from [Cp*RhX2]2 (X = Br, I) as well as the iridium species 13 and 14 derived from [Cp*IrCl2]2 are sufficiently stable and allow true carbene reactivity to be harnessed. These complexes are competent intermediates for the catalytic metathesis of azobenzene derivatives, which provides access to α-imino esters that would be difficult to make otherwise. Rather than involving metal nitrenes, the reaction proceeds via aza-ylides that evolve into diaziridines; a metastable compound of this type has been fully characterized.