Nitrogen-Rich Molybdenum Nitride Synthesized in a Crucible under Air.

The triple bond in N2 is significantly stronger than the double bond in O2, meaning that synthesizing nitrogen-rich nitrides typically requires activated nitrogen precursors, such as ammonia, plasma-cracked atomic nitrogen, or high-pressure N2. Here, we report a synthesis of nitrogen-rich nitrides under ambient pressure and atmosphere. Using Na2MoO4 and dicyandiamide precursors, we synthesized nitrogen-rich γ-Mo2N3 in an alumina crucible under an ambient atmosphere, heated in a box furnace between 500 and 600 °C. Byproducts of this metathesis reaction include volatile gases and solid Na(OCN), which can be washed away with water. X-ray diffraction and neutron diffraction showed Mo2N3 with a rock salt structure having cation vacancies, with no oxygen incorporation, in contrast to the more common nitrogen-poor rock salt Mo2N with anion vacancies. Moreover, an increase in temperature to 700 °C resulted in molybdenum oxynitride, Mo0.84N0.72O0.27. This work illustrates the potential for dicyandiamide as an ambient-temperature metathesis precursor for an increased effective nitrogen chemical potential under ambient conditions. The classical experimental setting often used for solid-state oxide synthesis, therefore, has the potential to expand the nitride chemistry.

Nickel Carbide Nanoparticle Catalyst for Selective Hydrogenation of Nitriles to Primary Amines.

Despite its unique physicochemical properties, the catalytic application of nickel carbide (Ni3 C) in organic synthesis is rare. In this study, we report well-defined nanocrystalline Ni3 C (nano-Ni3 C) as a highly active catalyst for the selective hydrogenation of nitriles to primary amines. The activity of the aluminum-oxide-supported nano-Ni3 C (nano-Ni3 C/Al2 O3 ) catalyst surpasses that of Ni nanoparticles. Various aromatic and aliphatic nitriles and dinitriles were successfully converted to the corresponding primary amines under mild conditions (1 bar H2 pressure). Furthermore, the nano-Ni3 C/Al2 O3 catalyst was reusable and applicable to gram-scale experiments. Density functional theory calculations suggest the formation of polar hydrogen species on the nano-Ni3 C surface, which were attributed to the high activity of nano-Ni3 C towards nitrile hydrogenation. This study demonstrates the utility of metal carbides as a new class of catalysts for liquid-phase organic reactions.

Iron phosphide nanocrystals as an air-stable heterogeneous catalyst for liquid-phase nitrile hydrogenation.

Iron-based heterogeneous catalysts are ideal metal catalysts owing to their abundance and low-toxicity. However, conventional iron nanoparticle catalysts exhibit extremely low activity in liquid-phase reactions and lack air stability. Previous attempts to encapsulate iron nanoparticles in shell materials toward air stability improvement were offset by the low activity of the iron nanoparticles. To overcome the trade-off between activity and stability in conventional iron nanoparticle catalysts, we developed air-stable iron phosphide nanocrystal catalysts. The iron phosphide nanocrystal exhibits high activity for liquid-phase nitrile hydrogenation, whereas the conventional iron nanoparticles demonstrate no activity. Furthermore, the air stability of the iron phosphide nanocrystal allows facile immobilization on appropriate supports, wherein TiO2 enhances the activity. The resulting TiO2-supported iron phosphide nanocrystal successfully converts various nitriles to primary amines and demonstrates high reusability. The development of air-stable and active iron phosphide nanocrystal catalysts significantly expands the application scope of iron catalysts.

A copper nitride nanocube catalyst for highly efficient hydroboration of alkynes.

The hydroboration of alkynes with bis(pinacolato)diboron is a useful method for the synthesis of vinyl boronate esters, which are essential intermediates in organic syntheses. Copper catalysts have been used extensively in these reactions. However, previously reported Cu-catalyst systems inevitably require additives and elevated temperatures. Herein, we report, for the first time, a simple and efficient hydroboration of alkynes under additive-free and mild reaction conditions (i.e., at a temperature of 30 °C) using a copper nitride nanocube (Cu3N NC) catalyst. A wide range of alkynes can be transformed into their corresponding boronate esters. Cu3N NCs are also applicable in the hydroboration of alkynes with tetrahydroxydiboron to synthesize vinyl boronic acids. Moreover, the Cu3N NCs were easily separated by simple filtration and could be reused several times without any loss of their original activity. Hence, these highly active and reusable Cu3N NC catalysts offer an environmentally friendly route for the efficient production of vinyl boronates.

Selective Hydrodeoxygenation of Esters to Unsymmetrical Ethers over a Zirconium Oxide-Supported Pt-Mo Catalyst.

The catalytic hydrodeoxygenation (HDO) of carbonyl oxygen in esters using H2 is an attractive method for synthesizing unsymmetrical ethers because water is theoretically the sole coproduct. Herein, we report a heterogeneous catalytic system for the selective HDO of esters to unsymmetrical ethers over a zirconium oxide-supported platinum-molybdenum catalyst (Pt-Mo/ZrO2). A wide range of esters were transformed into the corresponding unsymmetrical ethers under mild reaction conditions (0.5 MPa H2 at 100 °C). The Pt-Mo/ZrO2 catalyst was also successfully applied to the conversion of a biomass-derived triglyceride into the corresponding triether. Physicochemical characterization and control experiments revealed that cooperative catalysis between Pt nanoparticles and neighboring molybdenum oxide species on the ZrO2 surface plays a key role in the highly selective HDO of esters. This Pt-Mo/ZrO2 catalyst system offers a highly efficient strategy for synthesizing unsymmetrical ethers and broadens the scope of sustainable reaction processes.

Phosphorus-Alloying as a Powerful Method for Designing Highly Active and Durable Metal Nanoparticle Catalysts for the Deoxygenation of Sulfoxides: Ligand and Ensemble Effects of Phosphorus.

The modification of metal nanoparticles (NPs) by incorporating additional metals is a key technique for developing novel catalysts. However, the effects of incorporating nonmetals into metal NPs have not been widely explored, particularly in the field of organic synthesis. In this study, we demonstrate that phosphorus (P)-alloying significantly increases the activity of precious metal NPs for the deoxygenation of sulfoxides into sulfides. In particular, ruthenium phosphide NPs exhibit an excellent catalytic activity and high durability against sulfur-poisoning, outperforming conventional catalysts. Various sulfoxides, including drug intermediates, were deoxygenated to sulfides with excellent yields. Detailed investigations into the structure-activity relationship revealed that P-alloying plays a dual role: it establishes a ligand effect on the electron transfer from Ru to P, facilitating the production of active hydrogen species, and has an ensemble effect on the formation of the Ru-P bond, preventing strong coordination with sulfide products. These effects combine to increase the catalytic performance of ruthenium phosphide NPs. These results demonstrate that P-alloying is an efficient method to improve the metal NP catalysis for diverse organic synthesis.

Single-Crystal Cobalt Phosphide Nanorods as a High-Performance Catalyst for Reductive Amination of Carbonyl Compounds.

The development of metal phosphide catalysts for organic synthesis is still in its early stages. Herein, we report the successful synthesis of single-crystal cobalt phosphide nanorods (Co2P NRs) containing coordinatively unsaturated Co-Co active sites, which serve as a new class of air-stable, highly active, and reusable heterogeneous catalysts for the reductive amination of carbonyl compounds. The Co2P NR catalyst showed high activity for the transformation of a broad range of carbonyl compounds to their corresponding primary amines using an aqueous ammonia solution or ammonium acetate as a green amination reagent at 1 bar of H2 pressure; these conditions are far milder than previously reported. The air stability and high activity of the Co2P NRs is noteworthy, as conventional Co catalysts are air-sensitive (pyrophorous) and show no activity for this transformation under mild conditions. P-alloying is therefore of considerable importance for nanoengineering air-stable and highly active non-noble-metal catalysts for organic synthesis.

A nickel phosphide nanoalloy catalyst for the C-3 alkylation of oxindoles with alcohols.

Although transition metal phosphides are well studied as electrocatalysts and hydrotreating catalysts, the application of metal phosphides in organic synthesis is rare, and cooperative catalysis between metal phosphides and supports remains unexplored. Herein, we report that a cerium dioxide-supported nickel phosphide nanoalloy (nano-Ni2P/CeO2) efficiently promoted the C-3 alkylation of oxindoles with alcohols without any additives through the borrowing hydrogen methodology. Oxindoles were alkylated with various alcohols to provide the corresponding C-3 alkylated oxindoles in high yields. This is the first catalytic system for the C-3 alkylation of oxindoles with alcohols using a non-precious metal-based heterogeneous catalyst. The catalytic activity of nano-Ni2P/CeO2 was comparable to that reported for precious metal-based catalysts. Moreover, nano-Ni2P/CeO2 was easily recoverable and reusable without any significant loss of activity. Control experiments revealed that the Ni2P nanoalloy and the CeO2 support functioned cooperatively, leading to a high catalytic performance.

A copper nitride catalyst for the efficient hydroxylation of aryl halides under ligand-free conditions.

Copper nitride (Cu3N) was used as a heterogeneous catalyst for the hydroxylation of aryl halides under ligand-free conditions. The cubic Cu3N nanoparticles showed high catalytic activity, comparable to those of conventional Cu catalysts with nitrogen ligands, demonstrating that the nitrogen atoms in Cu3N act as functional ligands that promote hydroxylation.

Ni2 P Nanoalloy as an Air-Stable and Versatile Hydrogenation Catalyst in Water: P-Alloying Strategy for Designing Smart Catalysts.

Non-noble metal-based hydrogenation catalysts have limited practical applications because they exhibit low activity, require harsh reaction conditions, and are unstable in air. To overcome these limitations, herein we propose the alloying of non-noble metal nanoparticles with phosphorus as a promising strategy for developing smart catalysts that exhibit both excellent activity and air stability. We synthesized a novel nickel phosphide nanoalloy (nano-Ni2 P) with coordinatively unsaturated Ni active sites. Unlike conventional air-unstable non-noble metal catalysts, nano-Ni2 P retained its metallic nature in air, and exhibited a high activity for the hydrogenation of various substrates with polar functional groups, such as aldehydes, ketones, nitriles, and nitroarenes to the desired products in excellent yields in water. Furthermore, the used nano-Ni2 P catalyst was easy to handle in air and could be reused without pretreatment, providing a simple and clean catalyst system for general hydrogenation reactions.

Nickel phosphide nanoalloy catalyst for the selective deoxygenation of sulfoxides to sulfides under ambient H2 pressure.

Exploring novel catalysis by less common, metal-non-metal nanoalloys is of great interest in organic synthesis. We herein report a titanium-dioxide-supported nickel phosphide nanoalloy (nano-Ni2P/TiO2) that exhibits high catalytic activity for the deoxygenation of sulfoxides. nano-Ni2P/TiO2 deoxygenated various sulfoxides to sulfides under 1 bar of H2, representing the first non-noble metal catalyst for sulfoxide deoxygenation under ambient H2 pressure. Spectroscopic analyses revealed that this high activity is due to cooperative catalysis by nano-Ni2P and TiO2.

A cobalt phosphide catalyst for the hydrogenation of nitriles.

The study of metal phosphide catalysts for organic synthesis is rare. We present, for the first time, a well-defined nano-cobalt phosphide (nano-Co2P) that can serve as a new class of catalysts for the hydrogenation of nitriles to primary amines. While earth-abundant metal catalysts for nitrile hydrogenation generally suffer from air-instability (pyrophoricity), low activity and the need for harsh reaction conditions, nano-Co2P shows both air-stability and remarkably high activity for the hydrogenation of valeronitrile with an excellent turnover number exceeding 58000, which is over 20- to 500-fold greater than that of those previously reported. Moreover, nano-Co2P efficiently promotes the hydrogenation of a wide range of nitriles, which include di- and tetra-nitriles, to the corresponding primary amines even under just 1 bar of H2 pressure, far milder than the conventional reaction conditions. Detailed spectroscopic studies reveal that the high performance of nano-Co2P is attributed to its air-stable metallic nature and the increase of the d-electron density of Co near the Fermi level by the phosphidation of Co, which thus leads to the accelerated activation of both nitrile and H2. Such a phosphidation provides a promising method for the design of an advanced catalyst with high activity and stability in highly efficient and environmentally benign hydrogenations.

XAS Analysis of Reactions of (Arylimido)vanadium(V) Dichloride Complexes Containing Anionic NHC That Contains a Weakly Coordinating B(C6F5)3 Moiety (WCA-NHC) or Phenoxide Ligands with Al Alkyls: A Potential Ethylene Polymerization Catalyst with WCA-NHC Ligands.

(Arylimido)vanadium(V) dichloride complexes containing anionic N-heterocyclic carbene (NHC) ligands that contain weakly coordinating B(C6F5)3 moieties (WCA-NHC) of the type [V(NAr)Cl2(WCA-NHC-Ar')] (5, Ar = 2,6-Me2C6H3, Ar' = 2,6- i Pr2C6H3) showed significant catalytic activity for ethylene polymerization in the presence of Al cocatalysts (MAO and Al i Bu3); the activity by the 5-MAO catalyst (19 500 kg-PE/mol-V·h; TOF 11 600 min-1) is the highest among those reported using the other (imido)vanadium(V) complexes in the presence of MAO, and the 5-Al i Bu3 catalyst showed higher activity (66 000 kg-PE/mol-V·h; TOF 39 200 min-1). The V K-edge X-ray absorption near-edge structure (XANES) analyses (in toluene) strongly suggest the formation of certain vanadium(III) species by reduction with Al i Bu3 accompanying structural changes; the EXAFS analysis suggests the presence of the arylimido ligand and one V-Cl bond (2.34 ± 0.04 Å), which is longer than those [2.1901(8)-2.2462(8) Å] in the reported (imido)vanadium(V) complexes. The XANES analysis of [V(NAr)Cl2(OAr)] strongly suggests the formation of the other vanadium(III) species by reduction with Me2AlCl or Et2AlCl, and the EXAFS analysis suggests the presence of the arylimido ligand and two V-Cl bonds (2.45 ± 0.03 Å). The XANES spectra showed no significant changes in both the pre-edge peak(s) and the edge peak when these complexes were treated with MAO, suggesting that the basic geometry and the high oxidation state were preserved under these conditions.

New Routes for Refinery of Biogenic Platform Chemicals Catalyzed by Cerium Oxide-supported Ruthenium Nanoparticles in Water.

Highly selective hydrogenative carbon-carbon bond scission of biomass-derived platform oxygenates was achieved with a cerium oxide-supported ruthenium nanoparticle catalyst in water. The present catalyst enabled the selective cleavage of carbon-carbon σ bonds adjacent to carboxyl, ester, and hydroxymethyl groups, opening new eight synthetic routes to valuable chemicals from biomass derivatives. The high selectivity for such carbon-carbon bond scission over carbon-oxygen bonds was attributed to the multiple catalytic roles of the Ru nanoparticles assisted by the in situ formed Ce(OH)3.

Mild Hydrogenation of Amides to Amines over a Platinum-Vanadium Bimetallic Catalyst.

Hydrogenation of amides to amines is an important reaction, but the need for high temperatures and H2 pressures is a problem. Catalysts that are effective under mild reaction conditions, that is, lower than 30 bar H2 and 70 °C, have not yet been reported. Here, the mild hydrogenation of amides was achieved for the first time by using a Pt-V bimetallic catalyst. Amide hydrogenation, at either 1 bar H2 at 70 °C or 5 bar H2 at room temperature was achieved using the bimetallic catalyst. The mild reaction conditions enable highly selective hydrogenation of various amides to the corresponding amines, while inhibiting arene hydrogenation. Catalyst characterization showed that the origin of the catalytic activity for the bimetallic catalyst is the oxophilic V-decorated Pt nanoparticles, which are 2 nm in diameter.

Metal-Support Cooperative Catalysts for Environmentally Benign Molecular Transformations.

Metal-support cooperative catalysts have been developed for sustainable and environmentally benign molecular transformations. The active metal centers and supports in these catalysts could cooperatively activate substrates, resulting in high catalytic performance for liquid-phase reactions under mild conditions. These catalysts involved hydrotalcite-supported gold and silver nanoparticles with high catalytic activity for organic reactions such as aerobic oxidation, oxidative carbonylation, and chemoselective reduction of epoxides to alkenes and nitrostyrenes to aminostyrenes using alcohols and CO/H2 O as reducing reagents. This high catalytic performance was due to cooperative catalysis between the metal nanoparticles and basic sites of the hydrotalcite support. To increase the metal-support cooperative effect, core-shell nanostructured catalysts consisting of gold or silver nanoparticles in the core and ceria supports in the shell were designed. These core-shell nanocomposite catalysts were effective for the chemoselective hydrogenation of nitrostyrenes to aminostyrenes, unsaturated aldehydes to allyl alcohols, and alkynes to alkenes using H2 as a clean reductant. In addition, these solid catalysts could be recovered easily from the reaction mixture by simple filtration, and were reusable with high catalytic activity.

Synthesis and Structural Analysis of (Imido)vanadium Dichloride Complexes Containing 2-(2'-Benz-imidazolyl)pyridine Ligands: Effect of Al Cocatalyst for Efficient Ethylene (Co)polymerization.

(Imido)vanadium(V) dichloride complexes containing 2-(2'-benzimidazolyl)-6-methylpyridine ligand (L) of type V(NR)Cl2(L) [R = 1-adamantyl (Ad, 1), C6H5 (2), and 2,6-Me2C6H3 (3)] have been prepared, and their structures were determined by X-ray crystallography as distorted trigonal bipyramidal structures around vanadium. Reactions with ethylene using 1-3 in the presence of methylaluminoxane (MAO) afforded a mixture of oligomer and polymers, and the compositions were affected by the imido ligand employed. By contrast, 1-3 exhibited remarkable catalytic activities for ethylene polymerization in the presence of Me2AlCl; the phenylimido complex (2) exhibited the highest activity [80 100 kg-PE/mol-V·h turn over frequency (TOF, 2 850 000 h-1, 792 s-1)]. The ethylene copolymerizations with norbornene afforded ultrahigh-molecular-weight copolymers with uniform molecular weight distributions and compositions [e.g., M n = 1.71-2.66 × 106, M w/M n = 2.27-2.53]. On the basis of V nuclear magnetic resonance (51V NMR), electron spin resonance, and V K-edge X-ray absorption near-edge structure (XANES) spectra of the catalyst solution, the observed difference in the catalyst performance in the presence of (between) MAO and Me2AlCl cocatalyst should be due to the formation of different catalytically active species with different oxidation states. Apparent changes in the oxidation state were observed in the (especially in the NMR and XANES) spectra upon addition of Me2AlCl, whereas no significant changes in the spectra were observed in presence of MAO.

On-demand Hydrogen Production from Organosilanes at Ambient Temperature Using Heterogeneous Gold Catalysts.

An environmentally friendly ("green"), H2-generation system was developed that involved hydrolytic oxidation of inexpensive organosilanes as hydrogen storage materials with newly developed heterogeneous gold nanoparticle catalysts. The gold catalyst functioned well at ambient temperature under aerobic conditions, providing efficient production of pure H2. The newly developed size-selective gold nanoparticle catalysts could be separated easily from the reaction mixture containing organosilanes, allowing an on/off-switchable H2-production by the introduction and removal of the catalyst. This is the first report of an on/off-switchable H2-production system employing hydrolytic oxidation of inexpensive organosilanes without requiring additional energy.

Green, Multi-Gram One-Step Synthesis of Core-Shell Nanocomposites in Water and Their Catalytic Application to Chemoselective Hydrogenations.

We devise a new and green route for the multi-gram synthesis of core-shell nanoparticles (NPs) in one step under organic-free and pH-neutral conditions. Simply mixing core and shell metal precursors in the presence of solid metal oxides in water allowed for the facile fabrication of small CeO2 -covered Au and Ag nanoparticles dispersed on metal oxides in one step. The CeO2 -covered Au nanoparticles acted as a highly efficient and reusable catalyst for a series of chemoselective hydrogenations, while retaining C=C bonds in diverse substrates. Consequently, higher environmental compatibility and more efficient energy savings were achieved across the entire process, including catalyst preparation, reaction, separation, and reuse.

One-step Synthesis of Core-Gold/Shell-Ceria Nanomaterial and Its Catalysis for Highly Selective Semihydrogenation of Alkynes.

We report a facile synthesis of new core-Au/shell-CeO2 nanoparticles (Au@CeO2) using a redox-coprecipitation method, where the Au nanoparticles and the nanoporous shell of CeO2 are simultaneously formed in one step. The Au@CeO2 catalyst enables the highly selective semihydrogenation of various alkynes at ambient temperature under additive-free conditions. The core-shell structure plays a crucial role in providing the excellent selectivity for alkenes through the selective dissociation of H2 in a heterolytic manner by maximizing interfacial sites between the core-Au and the shell-CeO2.