Generating Parahydrogen-Induced Polarization Using Immobilized Iridium Complexes in the Gas-Phase Hydrogenation of Carbon–Carbon Double and Triple Bonds

Immobilized iridium complexes synthesized using [Ir(COD)Cl]₂ by anchoring on hydrous and anhydrous silica gels were studied in terms of generating parahydrogen-induced polarization (PHIP) in the gas-phase hydrogenation of propylene and propyne. Distinguishing differences in the hydrogenations of carbon–carbon double and triple bonds were found. It has been shown that in the double bond hydrogenation both catalysts are very active even at 25 °C. The reaction yield in continuous flow experiments is more than 70 %, whereas the obtained PHIP degrees are very low. In the case of the triple bond hydrogenation, a more or less active hydrogenation reaction was observed at relatively high temperatures (≈70–80 °C) for the catalyst immobilized on anhydrous silica, while the catalyst immobilized on hydrous silica was inactive at these temperatures. Contrary to the double bond hydrogenation, the triple bond hydrogenation provided significant signal enhancements observed in ¹H nuclear magnetic resonance spectra for the signals corresponding to protons of vinyl fragments of product propylene in both PASADENA and ALTADENA experiments. The catalyst, however, is not stable under the triple bond hydrogenation reaction conditions, and deactivates within several minutes. It was also found that at higher temperatures (100–120 °C), this catalyst demonstrates a reactivation most likely associated with the reduction of Ir(I) that results in the formation of Ir(0) surface metal nanoparticles.     

EXAFS study of model Pd/Ga2O3 catalysts for the liquid-phase hydrogenation of acetylene before and after the reaction

The catalytic characteristics of Pd/Ga₂O₃ samples in the liquid-phase hydrogenation of acetylene to ethylene are studied. The structure of the catalyst’s components before and after the reaction is examined by EXAFS spectroscopy. The activity of the original (after drying) samples results from the reduction of the original palladium oxide to a metallic state in the reaction medium. According to EXAFS, the catalysts reduced at 200°C contain small amounts of Pd-Ga alloy that was preserved in the reaction medium during the liquid-phase hydrogenation of acetylene and presumably increased the activity and selectivity of the samples.     

Understanding the leaching properties of heterogenized catalysts: a combined solid-state and PHIP NMR study

Para-hydrogen induced polarization (PHIP) NMR in solution, combined with solid-state NMR, can be efficiently employed for the highly sensitive in-situ detection of the leaching properties of immobilized catalysts. The knowledge of this property is important for possible applications of PHIP experiments in medicine, biology or industry, where leached catalysts poison the solution of hyperpolarized products. As experimental example Wilkinson's catalyst RhCl(PPh(3))(3) (1) immobilized on mesoporous silica is chosen. As model reaction the hydrogenation of styrene in solvents with different polarities (methanol-d(4), acetone-d(6) and benzene-d(6)) is used. A (31)P solid-state MAS-NMR study reveals that there are two different species of catalysts on the silica, namely coordinatively bound catalysts and physisorbed catalyst. Only the second species exhibits substantial leaching, which is visible in a strong PHIP enhancement of the reaction product.     

New investigations of technical rhodium and iridium catalysts in homogeneous phase employing para-hydrogen induced polarization

It is shown that the para-hydrogen induced polarization (PHIP) phenomenon in homogenous solution containing the substrate styrene is also observable employing simple inorganic systems of the form MCl₃·xH₂O (M=Rh, Ir) as catalyst. Such observation confirms that already very simple metal complexes enable the creation of PHIP signal enhancement in solution. This opens up new pathways to increase the sensitivity of NMR and MRT by PHIP enhancement using cost-effective catalysts and will be essential for further mechanistic studies of simple transition metal systems.     

Analysis of the ESR Spectrum of a Rhodium (II) Complex

Abstract

Rh(II) complexes are rather scarce¹ and often form dimeric structures, which are diamagnetic. The ESR spectra of definite Rh(II) species have so far been claimed for Rh in ZnWO₃ ², [Rh S₄C₄(CN)₄]^{2 ?}, ^3′4 [Rh(π-C₅H₅)₂]⁵, [(π-C₅H₅)Rh(π-C₂H₄)₂]⁺⁶, and an irradiation produced [RhCπ₂(CN)₄]^{2 ?} complex.⁷ A detailed analysis has been performed on the first², the second⁴ and the last⁷ complexes. The first system shows an almost axial symmetry and the unpaired electron has been assigned to the d_xy orbital² (the x,y,z axes are defined along the octahedral metal-ligand directions). The sulfur ligand complex and the dichlorotetracyano system have their unpaired electron in the d_Z ² orbital. ^4,7 In the course of studies ^8-10 on oxygenation of a Rh(I) complex, [RhCπ(C₈H₁₄)₂]₂, we observed ¹⁰ that a well defined ESR spectrum develops during the reaction in N,N′-dimethylacetamide (DMA) - lithium chloride media. For experimental detail, reference 10 should be consulted. The data summarized in the table refer to the spectrum B in that reference and are attributed to a Rh(II) species.     

Pd-Cu双金属催化剂上加氢反应的仲氢诱导超极化研究

本文通过多相催化-仲氢诱导超极化（HET-PHIP）核磁共振（NMR）技术研究了Pd-Cu/SiO₂双金属催化剂上丙炔选择性加氢反应.首先利用等体积浸渍法和连续浸渍法合成了一系列不同Pd/Cu比例和形貌的Pd-Cu/SiO₂双金属催化剂.通过ALTADENA（Adiabatic Longitudinal Transport After Dissociation Engenders Net Alignment）方法发现,催化剂的Pd/Cu比例和形貌均对PHIP的极化效率有较大影响.随着Pd-Cu双金属催化剂中Pd比例的增大,PHIP极化效率降低,同时反应活性增强.在同Pd/Cu比例下,相对于等体积浸渍法,连续浸渍法制备的层叠形貌催化剂具有较弱的极化效率以及较强的催化活性,这是由于催化剂表面暴露出的Pd数量增多,导致催化活性增强;同时单个Pd集簇表面积增大,使得氢原子移动范围扩大,从而造成极化效率降低.     

Evaluation of Activation Energies for Pairwise and Non-Pairwise Hydrogen Addition to Propyne Over Pd/Aluminosilicate Fiberglass Catalyst by Parahydrogen-Induced Polarization (PHIP)

Hydrogenation of propyne to propene over Pd/aluminosilicate fiberglass catalyst in the temperature range 175–350 °C was investigated with the use of parahydrogen-induced polarization (PHIP) technique. Activation energies for both pairwise and non-pairwise H₂ addition routes were estimated. It was found that at 175–275 °C the activation energies for hydrogen addition to the triple bond of propyne have similar values (about 60–70 kJ/mol) for both routes of hydrogen addition. At higher temperatures (275–350 °C), the rate constant for pairwise hydrogen addition reaches a maximum value while the rate constant for non-pairwise hydrogen addition continues to increase with increasing temperature.     

Asymmetric hydrogenation of (<Emphasis Type="Italic">E</Emphasis>)-dimethyl-2-acetamido-2-phenylvinylphosphonate in supercritical carbon dioxide in the presence of metal complex catalysts with phosphite-type ligands

Asymmetric hydrogenation of (E)-dimethyl-2-acetamido-2-phenylvinylphosphonate was performed in CH₂Cl₂ and supercritical carbon dioxide with the participation of Rh and Ir complexes with chiral phosphite-type ligands. Iridium catalysts dissolved in supercritical CO₂ allow high enantioselectivity (up to 98.5% ee) and conversion to be obtained. Rhodium catalysts yield exclusively racemic reaction products.     

Electronic structure and bond multiplicity in compounds of the type M2Rh2Ac4Cl2

The electronic structure of the binuclear complex Rh₂Ac₄Cl₂^2? was analysed using X-ray and X-ray photoelectron spectra. The closeness of the structure of Rh₂Ac₄Cl₂^2? to two boundary structures ClRhRhCl (I) and Cl… RhRh… Cl (II) has been studied. The correlation between Rh₂Ac₄ Cl₂^2? and RhCl₆^3? has shown that structure I is more in agreement with the experimental data than structure II. The structure of the K-edge of the spectra provides support for weakening of the RhCl bond.     

Iron-57 and iridium-193 Mössbauer spectroscopic studies of supported iron-iridium catalysts

⁵⁷Fe and¹⁹³Ir Mössbauer spectroscopy shows that silica- and alumina-supported iron-iridium catalysts formed by calcination in air contain mixtures of small particle iron (III) oxide and iridium(IV) oxide. The iridium dioxide in both supported catalysts is reduced in hydrogen to metallic iridium. The α-Fe₂O₃ in the silica supported materials is predominantly reduced in hydrogen to an iron-iridium alloy whilst in the alumina-supported catalyst the iron is stabilised by treatment in hydrogen as iron(II). Treatment of a hydrogen-reduced silica-supported iron catalyst in hydrogen and carbon monoxide is accompanied by the formation of iron carbides. Carbide formation is not observed when the iron-iridium catalysts are treated in similar atmospheres. The results from the bimetallic catalysts are discussed in terms of the hydrogenation of associatively adsorbed carbon monoxide and the selectivity of supported iron-iridium catalysts to methanol formation.     

The key Cl− ligand for metal‐to‐ligand charge transfer in mononuclear terpyridine ruthenium(II) and binuclear ruthenium(II) tetrapyridylpyrazine complexes

Electronic structures of binuclear ruthenium complexes [Ru₂(terpy)₂(tppz)]⁴⁺ ( 1A ) and [Ru₂Cl₂(L)₂(tppz)]²⁺ {L = bpy ( 2A ), phen ( 3A ), and dpphen ( 4A )} were studied by density functional theory calculations. Abbreviations of the ligands (Ls) are bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, dpphen = 4,7‐diphenyl‐1,10‐phenanthroline, terpy = 2,2′:6′,2″‐terpyridine, and tppz = tetrakis(2‐pyridyl)pyrazine. Their mononuclear reference complexes [Ru(terpy)₂]²⁺ ( 1B ) and [RuClL(terpy)]⁺ {L = bpy ( 2B ), phen ( 3B ), and dpphen ( 4B )} were also examined. Geometries of these mononuclear and binuclear Ru(II) complexes were fully optimized. Their geometric parameters are in good agreement with the experimental data. The binuclear complexes were characterized by electrospray ionization mass spectrometry, UV–Vis spectroscopy, and cyclic voltammograms. Hexafluorophosphate salts of binuclear ruthenium complexes of 3A and 4A were newly prepared. The crystal structure of binuclear complex 1A (PF₆)₄ was also determined. Orbital interactions were analyzed to characterize the metal‐to‐ligand charge‐transfer (MLCT) states in these complexes. The Cl^? ligand works to raise the orbital energy of the metal lone pair, which leads to the low MLCT state. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of bimetallic nanocompositions Au<Subscript>x</Subscript>Pd<Subscript>1-x</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> for catalytic CO oxidation

Colloidal suspensions of Au_xPd_1-x nanoalloys were prepared via hydrazine co-reduction of [AuCl₄]^? and [PdCl₄]^2? complex anions in aqueous solution. High molecular weight polymeric compounds polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and cryptoionic surfactants (AF-6 and AF-12 neonols, Triton X-100) were used as surface capping agents. Nanoparticles prepared under different experimental conditions were immobilized on γ-Al₂O₃ supports. The removal of the capping agents from the surface of the active particles was achieved through calcination of samples in oxidative atmosphere (air, 500 °C). This pretreatment of the catalysts significantly enhances their performance. Powder XRD, TEM, and EDX were employed to characterize the structure, size, and composition of the Au_xPd_1-x/γ-Al₂O₃ catalysts. The immobilized particles consist of uniformly mixed alloys having multi-domain face-centered cubic structure with typical crystallite size of 3–6 nm. The activity of the prepared samples was examined with temperature-programmed CO oxidation reaction (TP-CO+O₂). Triton X-100 surfactant is superior in a number of parameters. Among all Au_xPd_1-x/γ-Al₂O₃ catalysts tested, the one stabilized with Triton X-100 (0.4%Au-0.2%Pd@Triton X-100) was found to have the highest activity for conversion of CO into CO₂.     

Sonochemical synthesis and structural characterization of an organic-inorganic nanohybrid based on a copper-dithiocarbamate complex and PMo12O403− polyanion as a novel sonocatalyst

A new organic-inorganic nanohybrid compound, ([Cu{(HOCH₂CH₂)₂NCS₂}₂]₃[PMo₁₂O₄₀] (1)), has been prepared by sonochemical technique using copper(II) dithiocarbamate complex and a Keggin-type polyoxomolybdate in this research. FT-IR, XRD, FE-SEM, TEM, EDX, UV–Vis, TGA, BET, and single crystal XRD analyses were applied to describe the properties of the composition of the nanohybrid. Compound (1) is composed of [PMo₁₂O₄₀]^3– building blocks and [Cu{(HOCH₂CH₂)₂NCS₂}₂]¹⁺ cationic moieties, and electrostatic forces and substantial hydrogen-bonding interactions were applied to pack them; and consequently, a three dimensional supramolecular framework was made based on single-crystal X-ray diffraction patterns. FE-SEM and TEM images approved the morphology of the nanohybrid sample to be extremely penetrable. Very good sonocatalytic performance is shown by this supramolecular nanohybrid in the degradation of Rhodamine B (RhB), which is a cationic organic dye. The results showed complete degradation of cationic RhB (25 mg/L) within 70 min with the rate constant of 0.039min⁻¹ in the presence of nanohybrid (1) and H₂O₂ (4 mmol/L). Also, sonocatalytic activity of the nanohybrid (1) was higher than H₃PMo₁₂O₄₀, showing that the combining Cu(DEDTC)₂ complex with H₃PMo₁₂O₄₀ could be an excellent choice to improve its sonocatalytic activity. The used nanohybrid (1) can be recycled after easily removing from the reaction media by centrifuging, and there was no considerable loss of catalytic activity and retention of the structure.     

Photocatalytic degradation of BTEX using W-doped TiO2 immobilized on fiberglass cloth under visible light

W-doped TiO₂ were immobilized on fiberglass cloth (FGC). The catalyst possessed small crystallite sizes with a red-shift on an absorption edge. Good dispersion was observed over the immobilized catalyst. The photocatalytic degradation of gaseous BTEX was conducted in a flow reactor under day-light fluorescent. Parameters including gas flowrate, catalyst loading, initial concentration and relative humidity (%RH) were investigated. The prepared catalysts showed higher efficiency than that of TiO₂ approximately 18, 3, 3 and 2.5× for benzene, toluene, ethylbenzene and o-xylene, respectively. The condition to achieve 100% BTEX removal was found at 20 min/ml, catalyst loading 0.1 mg/cm² and 30% RH.     

Application of an Mn-MOF as a highly efficient catalyst for sunlight-driven hydrogen generation

ABSTRACT

Microscale crystals of a 2D layered Mn-MOF [Mn₂(TylP)₄]_n (TylP=5-(1,2,4-triazol-1-yl)isophthalic) with a thiolate-bridged binuclear Mn(II) node similar to the active site of the [MnAu]-hydrogenase were prepared. This material shows high catalytic activity for visible-light-driven hydrogen production under the illumination of white LED or direct sunlight. The turn-over frequency of the catalyst can reach up to 6?h^?1. In this study, the heterogeneous nature and recyclability of the catalyst, as well as the factors that affect the catalytic activity have been investigated and described. Moreover, the photocatalytic mechanism for the hydrogen generation of [Mn₂(TylP)₄]_n has also been proposed, based on fluorescence spectra and cyclic voltammetry.     

NMR Studies of the Reaction Path of the o-H2/p-H2 Spin Conversion Catalyzed by Vaska’s Complex in the Solid State

We have studied the o/p spin conversion of dihydrogen in contact with frozen solutions of Vaska’s complex Ir(CO)Cl(PPh₃)₂ (1) in C₆D₆ and with polycrystalline 1 at 77 K. The main purpose of this study was to elucidate the mechanism of this type of reactions found accidentally previously (Eisenschmid et al JACS 109:8089–8091, 1987 and Eisenberg ACS 24:110–116, 1991). The formation of p-H₂ was followed after thawing of the samples by ¹H nuclear magnetic resonance (NMR) spectroscopy at 298 K, where the oxidative addition of dihydrogen to 1 occurs leading to Vaska’s dihydride Ir(CO)ClH₂(PPh₃)₂ (2) which is known to exhibit para-hydrogen-induced polarization (PHIP). The PHIP signal was shown to be proportional to the concentration of p-H₂ as elucidated from the decrease of the signal of dissolved o-H₂. The reaction was found to be faster for the frozen solution as compared to the polycrystalline powder. Optical microscopy showed that small particles of 1 are separated from the solution during the freezing process, exhibiting a larger surface area as compared to the polycrystalline powder. When a mixture of H₂ and D₂ was exposed to the frozen solutions or to the polycrystalline powder, the formation of HD was observed by ¹H NMR. This finding indicates the presence of a chemical spin conversion involving two dihydrogen molecules. Additional ¹H NMR experiments of dihydrogen in frozen C₆D₆ at 110 K indicated the formation of larger pores containing gaseous H₂ as well as dihydrogen sites in interstitial sites between benzene molecules. Moreover, in the presence of 1, a signal at ?4.5 ppm was observed which was attributed to a dihydrogen in close contact with Ir.     

[Co(CO2)n]+团簇的红外解离光谱实验和理论研究

本文利用红外光解离光谱研究了一价钴阳离子与二氧化碳之间的相互作用. 通过密度泛函理论计算得到[Co(CO₂)_n]⁺团簇的几何结构,并且模拟了它们的振动光谱与实验数值进行比较. 研究结果表明,在[Co(CO₂)_n]⁺(n=2∽6)团簇中,钴阳离子通过电四极矩静电作用以端点结合的方式与二氧化碳中的氧原子结合在一起. 团簇的红外光谱都集中在二氧化碳反对称伸缩的波数附近,并且随着团簇尺寸的变化出现蓝移,最后把[Co(CO₂)_n]⁺的红外光解离光谱与稀有气体贴附的[Co(CO₂)_n]⁺-Ar的红外光解离光谱进行了比较.     

Rh基催化剂上氢甲酰化反应过程的原位高压NMR研究

制备了用于丙烯氢甲酰化反应的Rh/SBA-15 和PPh₃修饰的PPh₃-Rh/SBA-15催化剂. 应用原位变温高压核磁共振技术,对比研究了丙烯在Rh/SBA-15 和PPh₃修饰的多相催化剂PPh₃ Rh/SBA-15上的氢甲酰化反应,实现了高压条件下催化反应的原位固体核磁共振表征. ¹³C MAS NMR研究结果表明：在1.0 MPa的反应压力下,随着反应温度升高丙烯与合成气在Rh/SBA-15催化剂上可转化生成丁醛,而PPh₃配体修饰的PPh₃-Rh/SBA-15催化剂上丁醛产物的正异比显著提高.     

The synthesis and regeneration of palladium catalysts with the use of supercritical carbon dioxide

The solubility of palladium chloride complexes with organic ligands in supercritical carbon dioxide (SC-CO₂) was measured. The possibility of using SC-CO₂ as a working medium for the preparation and regeneration of deposited palladium catalysts was studied. The active catalyst component was deposited from solutions of palladium chloride complexes with organic ligands in SC-CO₂. The regeneration of catalysts deactivated during the hydrogenation of acetylene in an ethane-ethylene mixture was also performed in SC-CO₂ with varying process conditions. A comparison of the specific surface areas and activities of freshly prepared and regenerated samples showed that the methods suggested were highly competitive compared with the traditional regeneration techniques.     

Intramolecular electron transfer in mixed-valence complexes [(NH3)5Ru-L-Ru(NH3)5]5+ (L = N2, pyz, pym, 4,4’-bipy, bpa)

The dynamics of the intramolecular electron transfer from Ru(II) to Ru(III) in binuclear mixed-valence complexes [NH₃)₅Ru -L-Ru(NH₃)₅]⁵⁺ (L = N₂, pyz, bipy, pym, bpa) is analyzed by the semiempirical CINDO + CI method. Translated from ZhurnalStruktumoi Khimii, Vol. 39, No. 4, pp. 579–590, July–August, 1998.