The wet synthesis and quantification of ligand-free sub-nanometric Au clusters in solid matrices.

© The Royal Society of Chemistry. The synthesis of ligand-free sub-nanometric metal clusters on a large scale suffers typically from very low yields (15% yields, as unambiguously determined using a very simple and extremely sensitive analytical reaction test.

Metal–organic frameworks as chemical nanoreactors for the preparation of catalytically active metal compounds

Since the emergence of metal-organic frameworks (MOFs), a myriad of thrilling properties and applications, in a wide range of fields, have been reported for these materials, which mainly arise from their porous nature and rich host-guest chemistry. However, other important features of MOFs that offer great potential rewards have been only barely explored. For instance, despite the fact that MOFs are suitable candidates to be used as chemical nanoreactors for the preparation, stabilization and characterization of unique functional species, that would be hardly accessible outside the functional constrained space offered by MOF channels, only very few examples have been reported so far. In par…

Few layer 2D pnictogens catalyze the alkylation of soft nucleophiles with esters

Group 15 elements in zero oxidation state (P, As, Sb and Bi), also called pnictogens, are rarely used in catalysis due to the difficulties associated in preparing well–structured and stable materials. Here, we report on the synthesis of highly exfoliated, few layer 2D phosphorene and antimonene in zero oxidation state, suspended in an ionic liquid, with the native atoms ready to interact with external reagents while avoiding aerobic or aqueous decomposition pathways, and on their use as efficient catalysts for the alkylation of nucleophiles with esters. The few layer pnictogen material circumvents the extremely harsh reaction conditions associated to previous superacid–catalyzed alkylations…

Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids.

Metal single-atom catalysts (SACs) promise great rewards in terms of metal atom efficiency. However, the requirement of particular conditions and supports for their synthesis, together with the need of solvents and additives for catalytic implementation, often precludes their use under industrially viable conditions. Here, we show that palladium single atoms are spontaneously formed after dissolving tiny amounts of palladium salts in neat benzyl alcohols, to catalyze their direct aerobic oxidation to benzoic acids without ligands, additives, or solvents. With this result in hand, the gram-scale preparation and stabilization of Pd SACs within the functional channels of a novel methyl-cystein…

Cyclic metal(oid) clusters control platinum-catalysed hydrosilylation reactions : from soluble to zeolite and MOF catalysts

The Pt-catalysed addition of silanes to functional groups such as alkenes, alkynes, carbonyls and alcohols, i.e. the hydrosilylation reaction, is a fundamental transformation in industrial and academic chemistry, often claimed as the most important application of Pt catalysts in solution. However, the exact nature of the Pt active species and its mechanism of action is not well understood yet, particularly regarding regioselectivity. Here, experimental and computational studies together with an ad hoc graphical method show that the hydroaddition of alkynes proceeds through Pt-Si-H clusters of 3-5 atoms (metal(oid) association) in parts per million amounts (ppm), which decrease the energy of…

Cover Feature: Crystallographic Visualization of a Double Water Molecule Addition on a Pt 1 ‐MOF during the Low‐temperature Water‐Gas Shift Reaction (ChemCatChem 4/2021)

Stabilized Ru[(H2O)(6)](3+) in Confined Spaces (MOFs and Zeolites) Catalyzes the lmination of Primary Alcohols under Atmospheric Conditions with Wide Scope

[EN] Imines are ubiquitous intermediates in organic synthesis, and the metal-mediated imination of alcohols is one of the most direct and simple methods for their synthesis. However, reported protocols lack compatibility with many other functional groups since basic supports/media, pure oxygen atmospheres, and/or released hydrogen gas are required during reaction. Here we show that, in contrast to previous metal-catalyzed methods, hexa-aqueous Ru(III) catalyzes the imination of primary alcohols with very wide functional group tolerance, at slightly acid pH and under low oxygen atmospheres. The inorganic metal complex can be supported and stabilized, integrally, within either faujasite-type …

Self-assembly of catalytically-active supramolecular coordination compounds within metal-organic frameworks

[EN] Supramolecular coordination compounds (SCCs) represent the power of coordination chemistry methodologies to self-assemble discrete architectures with targeted properties. SCCs are generally synthesized in solution, with isolated fully coordinated metal atoms as structural nodes, thus severely limited as metal-based catalysts. Metal-organic frameworks (MOFs) show unique features to act as chemical nanoreactors for the in situ synthesis and stabilization of otherwise not accessible functional species. Here, we present the self-assembly of Pd-II SCCs within the confined space of a pre-formed MOF (SCCs@MOF) and its post-assembly metalation to give a Pd-II-Au-III supra molecular assembly, c…

Electrochemical monitoring of the oxidative coupling of alkynes catalyzed by triphenylphosphine gold complexes

Electrochemical monitoring of the oxidative coupling of alkynes in the homogeneous phase through catalytic cycles involving triphenylphosphine gold complexes and selectfluor as oxidant reveals that at least two gold species in +3 and +1 oxidation states are implicated. Electrochemically driven homocoupling of terminal alkynes using molecular oxygen as the oxidant can be performed using such catalysts. Keywords: Gold catalysis, Oxidative coupling of alkynes, Oxygen, Voltammetry

Gitteröffnung durch reduktive kovalente Volumen‐Funktionalisierung von schwarzem Phosphor

Eine chemisch-reduktive Volumen-Funktionalisierung von dünnlagigem schwarzem Phosphor (BP) gelang unter Verwendung von BP-Interkalationsverbindungen. Durch eine effektive reduktive Aktivierung wurde die kovalente Funktionalisierung des geladenen BP mit Alkylhalogeniden erzielt, wobei eine Öffnung des BP-Gitters und ein höherer Funktionalisierungsgrad als bei neutralen Reaktionsrouten resultieren.

Stabilized Naked Sub-nanometric Cu Clusters within a Polymeric Film Catalyze C-N, C-C, C-O, C-S, and C-P Bond-Forming Reactions

[EN] Sub-nanometric Cu clusters formed by endogenous reduction of Cu salts and Cu nanoparticles are active and selective catalysts for C−N, C−C, C−O, C−S, and C−P bond-forming reactions. Sub-nanometric Cu clusters have also been generated within a polymeric film and stored with full stability for months. In this way, they are ready to be used on demand and maintain high activity (TONs up to 104 ) and selectivity for the above reactions. A potential mechanism for the formation of the sub-nanometric clusters and their electronic nature is presented.

Crystallographic Visualization of a Double Water Molecule Addition on a Pt 1 ‐MOF during the Low‐temperature Water‐Gas Shift Reaction

[EN] The low-temperature water-gas shift reaction (WGSR, CO+H2O H-2+CO2) is considered a very promising reaction -candidate for fuel cells- despite an efficient and robust catalyst is still desirable. One of the more prominent catalysts for this reaction is based on single Pt atoms (Pt-1) on different supports, which are supposed to manifold the reaction by the accepted mechanism for the general WGSR, i. e. by addition of one H2O molecule to CO, with generation of CO2 and H-2. Here we show, experimentally, that not one but two H2O molecules are added to CO on the Pt-1 catalyst, as assessed by a combination of reactivity experiments with soluble Pt catalysts, kinetic and spectroscopic measur…

Gold Redox Catalytic Cycles for the Oxidative Coupling of Alkynes

[EN] Au(I)/Au(III) catalytic cycles are catalytically competent to perform the oxidative coupling of alkynes in the homogeneous phase at room temperature and without any protecting atmosphere. Selectfluor as oxidant, wet acetonitrile as solvent, and sodium carbonate as base are the reagents of choice. Both aromatic and alkyl alkynes can be coupled, and mechanistic studies reveal that at least two gold species having different oxidation states are implicated in the key step of the coupling.

The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry

The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd4 clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metal-organic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd4 c…

Lattice Opening upon Bulk Reductive Covalent Functionalization of Black Phosphorus

The chemical bulk reductive covalent functionalization of thin-layer black phosphorus (BP) using BP intercalation compounds has been developed. Through effective reductive activation, covalent functionalization of the charged BP by reaction with organic alkyl halides is achieved. Functionalization was extensively demonstrated by means of several spectroscopic techniques and DFT calculations; the products showed higher functionalization degrees than those obtained by neutral routes.

Unique distal size selectivity with a digold catalyst during alkyne homocoupling

Metal-catalysed chemical reactions are often controlled by steric hindrance around the metal atom and it is rare that substituents far away of the reaction site could be differentiated during reaction, particularly if they are simple alkyl groups. Here we show that a gold catalyst is able to discriminate between linear carbon alkynes with 10 or 12 atoms in the chain during the oxidative homocoupling of alkynes: the former is fully reactive and the latter is practically unreactive. We present experimental evidences, which support that the distal size selectivity occurs by the impossibility of transmetallating two long alkyl chains in an A-framed, mixed-valence digold (I, III) acetylide compl…

Cover Feature: Few‐layer Black Phosphorous Catalyzes Radical Additions to Alkenes Faster than Low‐valence Metals (ChemCatChem 8/2020)

Synthesis of Densely Packaged, Ultrasmall Pt02Clusters within a Thioether-Functionalized MOF: Catalytic Activity in Industrial Reactions at Low Temperature

The gram-scale synthesis, stabilization, and characterization of well-defined ultrasmall subnanometric catalytic clusters on solids is a challenge. The chemical synthesis and X-ray snapshots of Pt02 clusters, homogenously distributed and densely packaged within the channels of a metal-organic framework, is presented. This hybrid material catalyzes efficiently, and even more importantly from an economic and environmental viewpoint, at low temperature (25 to 140 °C), energetically costly industrial reactions in the gas phase such as HCN production, CO2 methanation, and alkene hydrogenations. These results open the way for the design of precisely defined catalytically active ultrasmall metal c…

Mixed component metal-organic frameworks: Heterogeneity andcomplexity at the service of application performances

The synthesis of mixed-component metal-organic frameworks (MOFs) –including multivariate MOFs (MTV-MOFs), multicomponent MOFs, mixed-metals MOFs and mixed-ligands and metals MOFs– is becoming a very active research field. This is mainly based on the unique possibilities these materials offer to incorporate multiple functionalities and in how this heterogenity and complexity is translated in unexpected properties, which are not just the sum of each component. This review critically encompasses the progress made in this field, covering the synthetic approaches, and specially focusing on the current reported applications –such as gas storage and separation, catalysis, luminescence, conductivit…

Selective Gold Recovery and Catalysis in a Highly Flexible Methionine-Decorated Metal–Organic Framework

A novel chiral 3D bioMOF exhibiting functional channels with thio-alkyl chains derived from the natural amino acid l-methionine (1) has been rationally prepared. The well-known strong affinity of gold for sulfur derivatives, together with the extremely high flexibility of the thioether "arms" decorating the channels, account for a selective capture of gold(III) and gold(I) salts in the presence of other metal cations typically found in electronic wastes. The X-ray single-crystal structures of the different gold adsorbates Au(III)@1 and Au(I)@1 suggest that the selective metal capture occurs in a metal ion recognition process somehow mimicking what happens in biological systems and protein r…

Acid Catalysis with Alkane/Water Microdroplets in Ionic Liquids

Ionic liquids are composed of an organic cation and a highly delocalized perfluorinated anion, which remain tight to each other and neutral across the extended liquid framework. Here we show that n-alkanes in millimolar amounts enable a sufficient ion charge separation to release the innate acidity of the ionic liquid and catalyze the industrially relevant alkylation of phenol, after generating homogeneous, self-stabilized, and surfactant-free microdroplets (1–5 μm). This extremely mild and simple protocol circumvents any external additive or potential ionic liquid degradation and can be extended to water, which spontaneously generates microdroplets (ca. 3 μm) and catalyzes Brönsted rather …

Confined Pt-1(1+) Water Clusters in a MOF Catalyze the Low-Temperature Water-Gas Shift Reaction with both CO2 Oxygen Atoms Coming from Water

[EN] The synthesis and reactivity of single metal atoms in a low-valence state bound to just water, rather than to organic ligands or surfaces, is a major experimental challenge. Herein, we show a gram-scale wet synthesis of Pt-1(1+) stabilized in a confined space by a crystallographically well-defined first water sphere, and with a second coordination sphere linked to a metal-organic framework (MOF) through electrostatic and H-bonding interactions. The role of the water cluster is not only isolating and stabilizing the Pt atoms, but also regulating the charge of the metal and the adsorption of reactants. This is shown for the low-temperature water-gas shift reaction (WGSR: CO + H2O CO2 + H…

Partial Reduction and Selective Transfer of Hydrogen Chloride on Catalytic Gold Nanoparticles

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim HCl in solution accepts electron density from Au NPs and partially reduces at room temperature, as occurs with other simple diatomic molecules, such as O2 and H2. The activation can be run catalytically in the presence of alkynes to give exclusively E-vinyl chlorides, after the regio- and stereoselective transfer of HCl. Based also on this method, vinyl chloride monomer (VCM) can be produced in a milder and greener way than current industrial processes.

MOF-Triggered Synthesis of Subnanometer Ag02 Clusters and Fe3+ Single Atoms: Heterogenization Led to Efficient and Synergetic One-Pot Catalytic Reactions

Isolated Fe(III)-O Sites Catalyze the Hydrogenation of Acetylene in Ethylene Flows under Front-End Industrial Conditions

[EN] The search for simple, earth-abundant, cheap, and nontoxic metal catalysts able to perform industrial hydrogenations is a topic of interest, transversal to many catalytic processes. Here, we show that isolated FeIII¿O sites on solids are able to dissociate and chemoselectively transfer H2 to acetylene in an industrial process. For that, a novel, robust, and highly crystalline metal¿organic framework (MOF), embedding FeIII¿OH2 single sites within its pores, was prepared in multigram scale and used as an efficient catalyst for the hydrogenation of 1% acetylene in ethylene streams under front-end conditions. Cutting-edge X-ray crystallography allowed the resolution of the crystal structur…

Exploring the Role of Amino Acid-Derived Multivariate Metal–Organic Frameworks as Catalysts in Hemiketalization Reactions

Click amidations, esterifications and one–pot reactions catalyzed by Cu salts and multimetal–organic frameworks (M–MOFs)

Amides and esters are prevalent chemicals in Nature, industry and academic laboratories. Thus, it is not surprising that a plethora of synthetic methods for these compounds has been developed along the years. However, these methods are not 100% atom economical and generally require harsh reagents or reaction conditions. Here we show a “spring–loaded”, 100% atom–efficient amidation and esterification protocol which consists in the ring opening of cyclopropenones with amines or alcohols. Some alkyl amines react spontaneously at room temperature in a variety of solvents and reaction conditions, including water at different pHs, while other alkyl amines, aromatic amines and alcohols react in th…

Few-layer Black Phosphorous Catalyzes Radical Additions to Alkenes Faster than Low-valence Metals

Abstract The substitution of catalytic metals by p‐block main elements has a tremendous impact not only in the fundamentals but also in the economic and ecological fingerprint of organic reactions. Here we show that few‐layer black phosphorous (FL‐BP), a recently discovered and now readily available 2D material, catalyzes different radical additions to alkenes with an initial turnover frequency (TOF0) up to two orders of magnitude higher than representative state‐of‐the‐art metal complex catalysts at room temperature. The corresponding electron‐rich BP intercalation compound (BPIC) KP6 shows a nearly twice TOF0 increase with respect to FL‐BP. This increase in catalytic activity respect to t…

Epoxidation vs. dehydrogenation of allylic alcohols: heterogenization of the VO(acac)2 catalyst in a metal–organic framework

Allylic alcohol epoxidation and dehydrogenation reactivity is distinguished when VO(acac)2 is used in solution or anchored in a metal–organic framework (MOF). The chemical mechanism depends on the electronic profile of alkene substituents when the vanadyl complex is used in the homogenous phase. However, confinement effects imparted by MOF channels allow gaining control of the chemoselectivity toward the dehydrogenation product.

Metal-Organic Frameworks as Chemical Nanoreactors: Synthesis and Stabilization of Catalytically Active Metal Species in Confined Spaces

ConspectusSince the advent of the first metal-organic frameworks (MOFs), we have witnessed an explosion of captivating architectures with exciting physicochemical properties and applications in a wide range of fields. This, in part, can be understood under the light of their rich host-guest chemistry and the possibility to use single-crystal X-ray diffraction (SC-XRD) as a basic characterization tool. Moreover, chemistry on preformed MOFs, applying recent developments in template-directed synthesis and postsynthetic methodologies (PSMs), has shown to be a powerful synthetic tool to (i) tailor MOFs channels of known topology via single-crystal to single-crystal (SC-SC) processes, (ii) impart…

Hydrolase–like catalysis and structural resolution of natural products by a metal–organic framework

[EN] The exact chemical structure of non-crystallising natural products is still one of the main challenges in Natural Sciences. Despite tremendous advances in total synthesis, the absolute structural determination of a myriad of natural products with very sensitive chemical functionalities remains undone. Here, we show that a metal-organic framework (MOF) with alcohol-containing arms and adsorbed water, enables selective hydrolysis of glycosyl bonds, supramolecular order with the so-formed chiral fragments and absolute determination of the organic structure by single-crystal X-ray crystallography in a single operation. This combined strategy based on a biomimetic, cheap, robust and multigr…

CCDC 1587822: Experimental Crystal Structure Determination

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CSD 1409698: Experimental Crystal Structure Determination

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CCDC 2090411: Experimental Crystal Structure Determination

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CCDC 1478222: Experimental Crystal Structure Determination

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CCDC 2122007: Experimental Crystal Structure Determination

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CCDC 1478221: Experimental Crystal Structure Determination

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CCDC 2107391: Experimental Crystal Structure Determination

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CCDC 1985884: Experimental Crystal Structure Determination

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CCDC 1478223: Experimental Crystal Structure Determination

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CCDC 1841391: Experimental Crystal Structure Determination

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CCDC 1517224: Experimental Crystal Structure Determination

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CCDC 1587821: Experimental Crystal Structure Determination

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CCDC 1841392: Experimental Crystal Structure Determination

Related Article: Miguel A. Rivero-Crespo, Marta Mon, Jesús Ferrando-Soria, Christian W. Lopes, Mercedes Boronat, Antonio Leyva-Pérez, Avelino Corma, Juan C. Hernández-Garrido, Miguel López-Haro, Jose J. Calvino, Enrique V. Ramos-Fernandez, Donatella Armentano, Emilio Pardo|2018|Angew.Chem.,Int.Ed.|57|17094|doi:10.1002/anie.201810251

CCDC 1985885: Experimental Crystal Structure Determination

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CCDC 1517225: Experimental Crystal Structure Determination

Related Article: Francisco R. Fortea-Pérez, Marta Mon, Jesús Ferrando-Soria, Mercedes Boronat, Antonio Leyva-Pérez, Avelino Corma, Juan Manuel Herrera, Dmitrii Osadchii, Jorge Gascon, Donatella Armentano and Emilio Pardo|2017|Nat.Mater|16|760|doi:10.1038/nmat4910

Cover Feature: Few‐layer Black Phosphorous Catalyzes Radical Additions to Alkenes Faster than Low‐valence Metals

The Cover Feature shows how phosphorene can catalyse different radical additions to alkenes. These catalysts have an initial turnover frequency up to two orders of magnitude higher than representative state–of–the–art metal complex catalysts at room temperature. In their Full Paper, M. Tejeda-Serrano et al. describe how the electron–richness of the 2D material, either phosphorene or graphene, parallels the catalytic activity of different low-valence iron compounds as metal catalysts. These results showcase the advantages of substituting metals by p–block main-group elements not only because of their positive economic and ecological fingerprint, but also because of their higher catalytic eff…