1,2,4-Triphospholyl gold(I) and copper(I) complexes: synthesis,crystal and molecular structures of [Cu(PMe3)2(μ-P3C2tBu2)(μ-I)Cu(PMe3)2], [Cu(PMe3)2(μ-P3C2tBu2)2Cu(PMe3)2] and [Au(η1-P3C2tBu2)2][Au(PEt3)2]

Treatment of K(P₃C₂^tBu₂) with Cu₂I₂ and PMe₃ gave the binuclear complex [Cu(PMe₃)₂(μ-P₃C₂^tBu₂)₂Cu(PMe₃)₂] via the isolated intermediate compound [Cu(PMe₃)₂(μ-P₃C₂^tBu₂)(μ-I)Cu(PMe₃)₂]. The reaction of K(P₃C₂^tBu₂) with [AuCl(PEt₃)] on the otherhand gave the cation:anion complex [Au(PEt₃)₂][Au(η¹-P₃C₂^tBu₂)₂]. All complexes were fully characterised by multinuclear spectroscopy and single crystal X-ray diffraction studies.     

Glycerol steam reforming over Ni–Fe–Ce/Al2O3 catalyst for hydrogen production

Research on Chemical Intermediates - In this study, we focused on the catalytic activity, stability, and kinetics of glycerol steam reforming (GSR) for the hydrogen production over...     

Picolinimidoamide-Cu(II) complex anchored on Fe3O4@SiO2 core–shell magnetic nanoparticles: an efficient reusable catalyst for click reaction

A Cu(II) complex supported on Fe₃O₄@SiO₂ core–shell magnetic nanoparticles (MNPs) was prepared and characterized by FT-IR, XRD, SEM, EDX, TEM, VSM, TGA, and AAS analysis. The load of Cu on picolinimidoamide ligand anchored on Fe₃O₄@SiO₂ core–shell MNPs was determined as 1.22, 1.54, and 1.70 wt% using AAS, EDX and TGA analyses, respectively. Synthesized Cu(II) complex on Fe₃O₄@SiO₂ MNPs efficiently catalyzed a click reaction between alkyl halides, alkynes, and sodium azide to synthesize corresponding triazoles in high to excellent yields. The catalyst was recovered using an external magnetic field, and recycled for subsequent reactions without substantial loss of efficiency.     

Fe3O4@SiO2@Propyl–ANDSA: as a new catalyst for one-pot synthesis of 4H-chromene

Research on Chemical Intermediates - This work describes a new method for a one-pot multicomponent condensation of a variety of aldehydes with dimedone and malononitrile in water, providing a...     

Preparation and characterization of SO4 2−/Fe2O3–TiO2–Nd2O3 catalyst

This paper reports on the preparation of SO₄ ^2?/Fe₂O₃–TiO₂–Nd₂O₃ (SFTN) by combustion method. The effect of Nd content on catalytic activity was investigated. The prepared materials doped and undoped by Nd were compared by means of TG-DTG, XRD, FT-IR, NH₃-TPD and TEM techniques. Results indicated that the introduction of Nd improved the catalytic activities of the catalysts. Catalytic activity of SFTN was the highest with 98.3 % menthol conversion when Nd content was at 2 wt%. The introduction of Nd stabilized the coordination bond between the sulfate irons and the metallic oxides, helping in the formation of solid acid sites, enhancing the dispersion of catalyst particles, and inhibiting the growth of catalyst particles under heating.     

MgCl(2)·4((CH(3))(2)CHCH(2)OH): A new molecular adduct for the preparation of TiCl(x)/MgCl(2) catalyst for olefin polymerization

A new molecular adduct of MgCl(2) with isobutanol, namely MgCl(2)·4((CH(3))(2)CHCH(2)OH) (MgiBOH), has been prepared as a precursor to the supporting material for an olefin polymerization catalyst. The MgiBOH adduct and final titanated Ziegler-Natta catalysts have been thoroughly characterized by powder XRD, thermal analysis, Raman spectroscopy and solid-state NMR for structural and spectroscopy aspects. A peak observed at 712 cm(-1) in the Raman spectra of MgiBOH indicates the characteristic Mg-O(6) breathing mode and the formation of the adduct. The diffraction feature at 2θ = 7.8° (d = 11.223 ?) in the XRD confirms the adduct formation and the layered structure. The aim of the present article is to study how the insertion of a bulky isobutanol moiety affects the structural and electronic properties of the MgCl(2)·isobutanol molecular adduct. Indeed, the focus of the present study is to explore how the presence of isobutanol, in the initial molecular adduct, influences the final Z-N catalyst properties and its activity.     

A water-stable metal-organic framework: serving as a chemical sensor of PO_4~(3–) and a catalyst for CO_2 conversion

A new 2D Eu-BTB framework(1) with stratified gridding structure of about 14.6×16.9was synthesized and characterized.Compound 1 displays excellent water stability with the pH 2–12. The luminescent investigations suggest that 1 could represent a chemical sensor of PO43. with high sensitivity and selectivity. Importantly, 1 as a sensor of PO_4~(3-) can be reused at least five times.On the other hand, the catalytic investigations of 1 were carried out, indicating that 1 could be demonstrated as a recyclable catalyst for CO_2 conversion with epoxides.     

The reaction of [W(PMe3)4(η2-CH2PMe2)H] with carbon dioxide and dihydrogen: characterisation of [{W(PMe3)3(η1-PMe2CH2)}2(C3H2O6)] using two-dimensional nuclear magnetic resonance spectroscopy

[W(PMe₃)₄(η²-CH₂PMe₂)H] reacts with a mixture of CO₂ and H₂ (1/1, 3 atm) at room temperature to give [W(PMe₃)₄H₂(η²-O₂CO)] and [{W(PMe₃)₃(η¹-PMe₂CH₂)}₂(C₃H₂O₆)]. [{W(PMe₃)₃(η¹-PMe₂CH₂)}₂(C₃H₂O₆)] has been characterised using two-dimensional homo- and hetero-nuclear correlation NMR techniques.     

One-dimensional heterobimetallic cyanide-bridged Fe(III)–Mn(II) complex: Synthesis,crystal structure,and magnetic properties

A new cyanide-bridged heterobimetallic Fe(III)–Mn(II) complex {[MnL][FebpdBrb]} [FebpdBrb]_n· 2nH₂O has been synthesized by using pyridinecarboxamide trans-dicyanideiron as the building block. The X-ray diffraction analysis has revealed the one-dimensional infinite structure of the complex consisting of the alternating [Mn(L)]²⁺ and [Fe(bpdBrb)(CN)₂]^– units forming a cyanide-bridged cationic polymeric chain, with [Fe(bpdBrb)(CN)₂]^– as the free anions. The antiferromagnetic coupling between the neighboring Fe(III) and Mn(II) ions through the bridging cyanide group has been revealed. The magnetic coupling constant has been determined as of J =–3.17 cm^–1.     

Synthesis and properties of a functionalized heterobimetallic Re(I)–Gd(III) complex as a potential dual-contrast agent for molecular imaging

In the design of dual-imaging probes, the first functionalized and neutral heterobimetallic Re(I)–Gd(III) complex, highly soluble in aqueous solutions, has been prepared. This system exhibits interesting photophysical properties (λ_em = 578 nm, ? = 1.4%) for optical imaging and substantial higher relaxivity (r₁ = 6.6 mM⁻¹ s⁻¹ at 0.47 T and 37 °C) than the clinically used MRI contrast agents. Moreover, this system incorporates an aromatic ester functionality suitable for bioconjugation.     

Magnetic core–shell Fe3O4@C-SO3H nanoparticle catalyst for hydrolysis of cellulose

Catalytic hydrolysis of cellulose over solid acid catalysts is one of efficient pathways for the conversion of biomass into fuels and chemicals. High catalytic activity and easy separation from reaction media are two important factors for evaluating the performance of the solid acid catalysts for the cellulose hydrolysis. In this study, we report a core–shell Fe₃O₄@C-SO₃H nanoparticle with a magnetic Fe₃O₄ core encapsulated in a sulfonated carbon shell, as recyclable catalyst for the hydrolysis of cellulose. The sulfonated carbon shell shows a good activity, presenting 48.6 % cellulose conversion with 52.1 % glucose selectivity under the moderate conditions of 140 °C after 12 h reaction. Importantly, the magnetic Fe₃O₄ core makes the catalysts easily separated from reaction mixtures by using the externally applied magnetic field. In addition, the Fe₃O₄@C-SO₃H nanoparticle catalyst shows a high stability in the activity and magnetization during recycling tests, suggesting it a promising solid acid catalyst for the hydrolysis of cellulose.     

Chitosan–silica nanoparticles catalyst (M@CS–SiO2) for the degradation of 1,1-dimethylhydrazine

Research on Chemical Intermediates - Hybrid materials of chitosan–silica (CS–SiO2) with nonprecious-metallic ions (Cu) immobilized on (Cu–M@CS–SiO2) were developed as green...     

Cyanide-bridged bi- and trinuclear heterobimetallic Fe(III)–Mn(III) complexes: Synthesis,crystal structures and magnetic properties

By employing trans-dicyano or pentacyanometalate as building block and using a bicompartimental Schiffbase based manganese(III) compound as assemble segment, two new cyanide-bridged heterometallic Fe(III)–Mn(III) complexes {[Mn(L)(H₂O)][Febpb(CN)₂]}·2CH₃OH (1) and {[Mn(L)(H₂O)]₂··[Fe(CN)₅NO]} (2) (bpb^2– = 1,2-bis(pyridine-2-carboxamido)benzenate, L = N,N'-ethylene-bis(3-ethoxysalicylideneiminate) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single X-ray diffraction analysis reveals binuclear FeMn and trinuclear FeMn₂ structure, respectively, in which the cyanide precursor acts as mono- or bidentate ligand to connect the Mn(III) Schiff-base unit(s). Furthermore, these two complexes are self-complementary through coordinated aqua ligands from one complex and the free O₄ compartments from the neighboring complex, giving dimeric and 1D single chain supramolecular structure. Investigation of the magnetic susceptibility of 1 reveals weak antiferromagnetic coupling between the adjacent Mn(III) ions. Based on the binuclear FeMn model, best fit of the magnetic susceptibilities of 1 leads to the magnetic coupling constants J =–1.37 cm^–1 and zJ′ =–0.72 cm^–1 (1).     

Autonomous oscillating microgels involving Fe(phen)3 catalyst synchronized with the Belousov–Zhabotinsky reaction

A novel kind of microgels’ poly(NIPAAm-co-Fe(phen)₃-co-CS) were prepared by copolymerization of N-isopropylacrylamide (NIPAAm), chitosan (CS), and iron(II) 5-acrylamide-1,10-phenanthroline-bis(1,10-phenanthroline) (denoted as Fe(phen)₃), the catalyst for the Belousov–Zhabotinsky (BZ) reaction. The microgels were characterized by FTIR spectroscopy, scanning electron microscope, and static water contact angle. In addition, the self-oscillating behaviors of the microgels were investigated in BZ system free of catalyst. Both the redox potential and transmittance self-oscillation were observed. Moreover, the self-oscillating parameters, such as the induction period, oscillating period, duration, and amplitude decreased with the increasing of CS contents. This special property enables them to be used as biocompatible materials for a variety of applications.     

L-Tyrosine-Pd complex supported on Fe3O4 magnetic nanoparticles: A new catalyst for C–C coupling and Synthesis of sulfides

In the present work, Fe₃O₄@L-Tyrosine-Pd heterogeneous nanocatalyst was prepared by a simple and inexpensive procedure. The prepared nanocatalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray Diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma optical emission spectroscopy (ICP-OES), scanning electron microscopy (SEM), Transmission electron microscopy)TEM(, X-ray mapping, thermal gravimetric analysis (TGA), N₂ adsorption and desorption (BET) and vibrating sample magnetometer (VSM) techniques. Besides, it was employed as an efficent catalyst for C-C cross coupling and S-arylation reactions under green conditions. The optimized conditions for these reactions are described. The heterogeneous catalyst can be easily separated by applying a simple magnet and can also be reused in several consecutive runs without appreciable change in its catalytic activity.     

Tuning the electronic properties of Fe2(μ-arenedithiolate)(CO)6−n(PMe3)n (n = 0, 2) complexes related to the [Fe–Fe]-hydrogenase active site

Complexes [Fe₂(μ-S₂Ar)(CO)₆] (S₂Ar) = benzene-1,2-dithiolate (1a) toluene-3,4-dithiolate (2a), 3,6-dichloro-1,2-benzenedithiolate (3a), quinoxaline-2,3-dithiolate (7a) have been prepared to investigate the electronic effect that different bridging arenedithiolate ligands have on the appended Fe₂(CO)₆ sites. Dinuclear complexes [Fe₂(μ-S₂Ar)(CO)₄(PMe₃)₂] (1–3,7)b and mononuclear complexes [Fe(S₂Ar)(CO)₂(PMe₃)₂] (1–3,7)c were synthesized from their parent hexacarbonyl complexes (1–3,7)a. IR spectroscopic, crystallographic and electrochemical analyses show that an increase of the electron-withdrawing character (where quinoxaline-2,3-dithiolate > 3,6-dichloro-1,2-benzenedithiolate > 1,2-benzenedithiolate ≥ toluene-3,4-dithiolate) of the bridging ligand leads to a decreased electron density at the iron centers, which yield a milder reduction potential and higher eCO stretching frequencies. This effect is coherent for all of the investigated complexes. Electrocatalytic proton reduction by complex 3a (with trifluoromethanesulfonic acid) was evidenced by cyclic voltammetry. As a result of the milder reduction potential of 3a itself, proton reduction that is promoted by 3a proceeds at a potential that is milder than that for the 1a-catalyzed process.     

A disulfide-bridged manganese carbonyl anion: synthesis,structure and reactivity of [Mn3(CO)10(μ3-S2)2]−

The reduction of Mn₂(CO)₇(μ-S₂), (1) with sodium amalgam in THF provided the new monoanion [Mn₃(CO)₁₀(μ₃-S₂)₂]⁻, (3) isolated in low yield as the [Ph₃PMe] salt. The reaction of Mn₄(CO)₁₅(μ₃-S₂)(μ₄-S₂), (2) with [Ph₃PMe]I provided the same salt [Ph₃PMe] [3] in a good yield, 68%. Anion 3 reacts [CpFe(CO)₂(acetone)]BF₄ to yield the neutral mixed metal complex CpFeMn₃(CO)₁₂(μ₃-S₂)(μ₄-S₂), (4). The structures of [Ph₃PMe] [3] and 4 were determined by single crystal X-ray diffraction analyses. The core of the structure of 3 consists of two [Mn(CO)₃] groups bridged by two disulfido ligands in a μ₂–η² fashion with an additional [Mn(CO)₄] group that bridges the two disulfido ligands. The CpFe(CO)₂ group in 4 is bonded to a sulfur atom of one of the two disulfido ligands of the anionic grouping of 3.     

Nano 5% Fe–ZnO: A highly efficient and recyclable heterogeneous solid nano catalyst for the Biginelli reaction

In this paper, we report the synthesis and catalytic application of 5% Fe–ZnO nanocatalyst for the synthesis of 3,4-dihydropyrimidin-2-one derivatives as a highly efficient heterogeneous nanocatalyst. The structural and morphological features of the synthesized nanocatalysts were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Using Debye-Scherer's formula, the average particle size for undoped ZnO was calculated to be 24.55 nm, while the average particle size for 5% Fe–ZnO was calculated to be 22.37 nm. The high resolution transmission electron microscopy (HR-TEM) revealed a hexagonal crystal lattice type. The Brunauer–Emmett–Teller (BET) surface area of ZnO and 5% Fe–ZnO was found to be 56.50 m²/g and 72.65 m²/g, respectively. Energy Dispersive X-Ray Analysis (EDX) confirmed the elemental composition of undoped ZnO and doped 5% Fe–ZnO nanocatalysts. Biginelli products were produced using a one-pot three-component reaction of urea, β-dicarbonyl compound, and various aromatic aldehydes using 5% Fe–ZnO under clean conditions. It was found that a 5% Fe–ZnO nanocatalyst is a highly efficient heterogeneous nanocatalyst for the synthesis of 3,4-dihydropirimidinones. ¹H NMR and ¹³C NMR analysis was used to confirm the structure of the synthesized Biginelli adducts. This synthetic protocol offers several advantages, including a short reaction time and purity of the synthesized, reusability and ease of catalyst separation, and a clean and quick workup.     

Fe(II)LSCo(III)LS]2 ⇔ [Fe(III)LSCo(II)HS]2 photoinduced conversion in a cyanide-bridged heterobimetallic molecular square

The self-assembly of [Fe(III){B(pz)(4)}(CN)(3)](-) and [Co(II)(bik)(2)(S)(2)](2+) affords the diamagnetic cyanide-bridged [Fe(II)(LS)Co(III)(LS)](2) molecular square which is converted into the corresponding magnetic [Fe(III)(LS)Co(II)(HS)](2) species under light irradiation at relatively low temperatures.