Phenalenyl‐Based Organozinc Catalysts for Intramolecular Hydroamination Reactions: A Combined Catalytic,Kinetic, and Mechanistic Investigation of the Catalytic Cycle

Herein, we report the synthesis and characterization of two organozinc complexes that contain symmetrical phenalenyl (PLY)‐based N,N‐ligands. The reactions of phenalenyl‐based ligands with ZnMe₂ led to the formation of organozinc complexes [N(Me),N(Me)‐PLY]ZnMe ( 1 ) and [N(iPr),N(iPr)‐PLY]ZnMe ( 2 ) under the evolution of methane. Both complexes ( 1 and 2 ) were characterized by NMR spectroscopy and elemental analysis. The solid‐state structures of complexes 1 and 2 were determined by single‐crystal X‐ray crystallography. Complexes 1 and 2 were used as catalysts for the intramolecular hydroamination of unactivated primary and secondary aminoalkenes. A combined approach of NMR spectroscopy and DFT calculations was utilized to obtain better insight into the mechanistic features of the zinc‐catalyzed hydroamination reactions. The progress of the catalysis for primary and secondary aminoalkene substrates with catalyst 2 was investigated by detailed kinetic studies, including kinetic isotope effect measurements. These results suggested pseudo‐first‐order kinetics for both primary and secondary aminoalkene activation processes. Eyring and Arrhenius analyses for the cyclization of a model secondary aminoalkene substrate afforded ΔH^≠=11.3 kcal mol^?1, ΔS^≠=?35.75 cal K^?1 mol^?1, and E_a=11.68 kcal mol^?1. Complex 2 exhibited much‐higher catalytic activity than complex 1 under identical reaction conditions. The in situ NMR experiments supported the formation of a catalytically active zinc cation and the DFT calculations showed that more active catalyst 2 generated a more stable cation. The stability of the catalytically active zinc cation was further supported by an in situ recycling procedure, thereby confirming the retention of catalytic activity of compound 2 for successive catalytic cycles. The DFT calculations showed that the preferred pathway for the zinc‐catalyzed hydroamination reactions is alkene activation rather than the alternative amine‐activation pathway. A detailed investigation with DFT methods emphasized that the remarkably higher catalytic efficiency of catalyst 2 originated from its superior stability and the facile formation of its cation compared to that derived from catalyst 1 .     

Electrochemically reduced tungsten‐based active species as catalysts for cross‐metathesis reactions: cross‐metathesis of non‐functionalized olefins

The electrochemical reduction of WCl₆ results in the formation of an active olefin (alkene) metathesis catalyst. The application of the WCl₆–e^?–Al–CH₂Cl₂ catalyst system to cross‐metathesis reactions of non‐functionalized acyclic olefins is reported. Undesirable reactions, such as double‐bond shift isomerization and subsequent metathesis, were not observed in these reactions. Cross‐metathesis of 7‐tetradecene with an equimolar amount of 4‐octene generated the desired cross‐product, 4‐undecene, in good yield. The reaction of 7‐tetradecene with 2‐octene, catalyzed by electrochemically reduced tungsten hexachloride, resulted in both self‐ and cross‐metathesis products. The cross‐metathesis products, 2‐nonene and 6‐tridecene, were formed in larger amounts than the self‐metathesis products of 2‐octene. The optimum catalyst/olefin ratio and reaction time were found to be 1 : 60 and 24 h, respectively. The cross‐metathesis of symmetrical olefins with α‐olefins was also studied under the predetermined conditions. Copyright © 2003 John Wiley & Sons, Ltd.     

Careful investigation of the hydrosilylation of olefins at poly(ethylene glycol) chain ends and development of a new silyl hydride to avoid side reactions

Hydrosilylation of olefin groups at poly(ethylene glycol) chain ends catalyzed by Karstedt catalyst often results in undesired side reactions such as olefin isomerization, hydrogenation, and dehydrosilylation. Since unwanted polymers obtained by side reactions deteriorate the quality of end‐functional polymers, maximizing the hydrosilylation efficiency at polymer chain ends becomes crucial. After careful investigation of the factors that govern side reactions under various conditions, it was related that the short lifetime of the unstable Pt catalyst intermediate led to the formation of more side products under the inherently dilute conditions for polymers. Based on these results, two new chelating hydrosilylation reagents, tris(2‐methoxyethoxy)silane (5) and 2,10‐dimethyl‐3,6,9‐trioxa‐2,10‐disilaundecane (6), have been developed. It was demonstrated that the hydrosilylation efficiency at polymer chain ends was significantly increased by employing the internally coordinating hydrosilane 5. In addition, employment of the internally coordinating disilane species 6 in an addition polymerization with 1,5‐hexadiene by hydrosilylation reaction yielded a polymer with high molecular weight (M_n = 9300 g/mol), which was significantly higher than that (M_n = 2600 g/mol) of the corresponding polymer obtained with non‐chelating dihydrosilane, 1,1,3,3‐tetramethyldisiloxane. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 527–536     

工业Fe-Mn催化剂上基于详细反应机理的F-T合成动力学模型Ⅱ.不同校正方法的动力学模型分析

 通过平衡闪蒸模拟催化剂孔道液体组成、烯烃物理吸附和虚拟烯烃分压等方法,考察了化学反应以外的非本征因素对F-T合成动力学模型的校正. 平衡闪蒸模拟催化剂孔道中烯烃组成的校正计算结果表明,在烯烃浓度出现峰值前,溶解度效应对烯烃再吸附及参与二次反应起主导作用,而在烯烃浓度出现峰值后,烯烃的扩散和物理吸附等效应可能起主导作用. 分析烯烃添加的反应器模拟结果发现,考虑烯烃物理吸附作用的动力学模型校正方法不能够正确反映烯烃添加实验的定性规律,而虚拟烯烃分压校正方法能够正确反映烃分布规律并可定量预测烯烃添加对产物分布规律的影响,这对需要尾气循环的F-T合成工业操作具有重要意义.     

Kinetics of the reaction of 4,4′‐biphenol with bromoethane and 1‐bromobutane by phase‐transfer catalysis

The reaction of 4,4′‐biphenol and two species of bromoalkanes (e.g., bromoethane and 1‐bromobutane) to synthesize two symmetric products (4,4′‐diethanoxy biphenyl and 4,4′‐dibutanoxy biphenyl) and one asymmetric product (4‐ethanoxy, 4′‐butanoxy biphenyl) was successfully carried out under two‐phase phase‐transfer catalysis conditions. A rational mechanism and kinetic model were built up by considering the reactions both in aqueous phase and in organic phase. The first active catalyst (QO(Ph)₂OQ) was also synthesized under two‐phase reaction and was identified by instruments. The experimental data were explained satisfactorily by the pseudo‐steady‐state hypothesis. Two sets of rate constants of organic reactions, i.e. primary (k₁ and k₂) and secondary (k₁₁, k₁₂, k₂₁, and k₂₂) rate constants participate in the kinetic model. The two primary rate constants were obtained individually via experimental data for synthesizing the symmetric products. The ratios of the other four secondary rate constants were obtained from the reaction of synthesizing asymmetric products and determined from the initial yield rates of symmetric products. The effects of the ratio of bromoethane and 1‐bromobutane, temperature, organic solvents, amount of catalyst, and amount of sodium hydroxide on the reaction rate and the selectivity of products were investigated in detail. The results were explained satisfactorily by the interaction between the reactants and the environmental species. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 139–153, 2003     

Alumina-supported iron catalyst - long-term study of the light product distribution in Fischer-Tropsch synthesis

Several models have been proposed to describe the carbon number product distribution and mechanism in Fischer-Tropsch synthesis (FTS). However, these models have not fully explained the product distribution and mechanism owing to the wide range and complexity of hydrocarbons in FTS. This study was conducted based on the Yao and Anderson-Schulz-Flory (ASF) carbon number product distribution models for light (C₁–C₆) hydrocarbon products of a Fe/Al₂O₃ catalyst. The product distribution based on the molar ratio of olefin to paraffin (O/P) and the neighboring olefins was also studied in order to better understand the mechanism in FTS and C₂ olefin deviation during FTS.Two sets of experiments (A and B) with different reaction conditions were conducted in microtubular fixed-bed reactors on the Fe/Al₂O₃ catalyst for 2249 h and 360 h, respectively. We found that the α values from the Yao and ASF carbon number product distribution models are relatively similar. The α values from the Yao carbon number product distribution plots are relatively constant, irrespective of the reaction conditions.Interestingly, it was also found that the secondary reactions of the C₂ olefin by re-adsorption to produce paraffins and long-chain olefins are dependent on the CO conversion and the reaction temperature during the FTS. Also, the product distribution of the neighboring olefins during the reduction condition gave a similar trend to what was observed for other reaction conditions. This result confirmed what was observed in the Yao and ASF carbon number product distribution of the olefins.     

The Role of Pd2+/Pd0 in Hydrogenation by [Pd(2‐pymo)2]n: An X‐ray Absorption and IR Spectroscopic Study

The metal–organic framework (MOF) [Pd(2‐pymo)₂]_n (2‐pymo=2‐pyrimidinolate) was used as catalyst in the hydrogenation of 1‐octene. During catalytic hydrogenation, the changes at the metal nodes and linkers of the MOF were investigated by in situ X‐ray absorption spectroscopy (XAS) and IR spectroscopy. With the help of extended X‐ray absorption fine structure and X‐ray absorption near edge structure data, Quick‐XAS, and IR spectroscopy, detailed insights into the catalytic relevance of Pd²⁺/Pd⁰ in the hydrogenation of 1‐octene could be achieved. Shortly after exposure of the catalyst to H₂ and simultaneously with the hydrogenation of 1‐octene, the aromatic rings of the linker molecules are hydrogenated rapidly. Up to this point, the MOF structure remained intact. After completion of linker hydrogenation, the linkers were also protonated. When half of the linker molecules were protonated, the onset of reduction of the Pd²⁺ centers to Pd⁰ was observed and the hydrogenation activity decreased, followed by fast reduction of the palladium centers and collapse of the MOF structure. Major fractions of Pd⁰ are only observed when the hydrogenation of 1‐octene is almost finished. Consequently, the Pd²⁺ nodes of the MOF [Pd(2‐pymo)₂]_n are identified as active centers in the hydrogenation of 1‐octene.     

Catalytic olefin hydrogenation with the application of a new water soluble rhodium catalyst

The catalyst precursor preparedin situ from rhodium dimer [Rh(cod)Cl]₂ and a new water-soluble phosphine Ph₂PCH₂CH₂CONHC(CH₃)₂CH₂SO₃H (in Li⁺ salt form) has been found to act as an effective olefin hydrogenation catalyst. Catalytic hydrogenation reactions have been tested in either two phase: aqueous catalyst/insoluble olefin or methanolic catalyst/olefin systems. The observed reaction rates were higher for terminal than for internal olefins. 1-Hexene in methanolic solution has been hydrogenated with a turnover frequency of about 8000 h^–1. This system has also been applied in the form of a supported aqueous phase catalyst.     

Synthesis of cyclic olefin polymers with high glass transition temperature by ring‐opening metathesis copolymerization and subsequent hydrogenation

Novel cyclic olefin polymers (COPs) derived from bulky cyclic olefin, exo‐1,4,4a,9,9a,10‐hexahydro‐9,10(1′,2′)‐benzeno‐l,4‐methanoanthracene (HBMN), with high glass transition temperature (T_g), excellent thermal stability, high transparency, and improved mechanical performance, have been achieved by ring‐opening metathesis polymerization and subsequent hydrogenation. The “first‐generation Grubbs” catalyst, RuCl₂(PCy₃)₂(CHPh) (Cy = cyclohexyl) ( G1 ), displays very high activity for homo/copolymerization with complete conversion. Homopolymer of the HBMN after complete hydrogenation showed a highest T_g of 223.6 °C. Copolymerization of HBMN with tricyclo[4.3.0.12,5]deca‐3‐ene or 5‐n‐hexylnorbornene was also carried out. These two series of COPs were characterized by gel permeation chromatography, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. The T_g of the resulted COPs linearly increased with HBMN content, which is easily controlled by changing feed ratios. The tensile test indicates that these copolymers have good mechanical performance as all these copolymers show a higher strain at break compared with commercial products (TOPAS^®). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2654‐2661     

用UBI-QEP方法分析钴系Fischer-Tropsch合成催化反应机理

采用unity bond index-quadratic exponential potential(UBI-QEP)方法, 以Co(0001) 单晶为模型催化剂, 对Fischer-Tropsch(F-T)合成的三种可能反应机理(表面碳化物机理、烯醇机理和CO插入机理)进行了全面的能学分析. 计算结果表明, 通过表面碳化物机理生成烃类产物从能学角度看较为合理, 其中CO_ads表面解离和C_ads加氢具有较高的活化能垒, 可能是整个F-T反应序列中的慢步骤; 通过CH_2,ads插入金属-烷基键实现链增长的活化能垒最低, 是能量上有利的链增长方式; 在Co(0001)晶面上烷基经β-H消除生成烯烃的活化能垒低于加氢生成烷烃, 而通过CO插入机理生成的有机含氧化合物的二次反应能垒较低, 从而导致其在Co催化剂上的低选择性. 此外, 与Fe/W(110)相比, Co金属上的CH_x,ads加氢以及CH_2,ads插入的活化能垒较低, 从而解释了Co催化剂上甲烷选择性较高和倾向于生成重质烃类产物的特性.     

Kinetics of ethylene polymerization reactions with chromium oxide catalysts

Principal kinetic data are presented for ethylene homopolymerization and ethylene/1‐hexene copolymerization reactions with two types of chromium oxide catalyst. The reaction rate of the homopolymerization reaction is first order with respect to ethylene concentration (both for gas‐phase and slurry reactions); its effective activation energy is 10.2 kcal/mol (42.8 kJ/mol). The r₁ value for ethylene/1‐hexene copolymerization reactions with the catalysts is ～30, which places these catalysts in terms of efficiency of α‐olefin copolymerization with ethylene between metallocene catalysts (r₁ ～ 20) and Ti‐based Ziegler‐Natta catalysts (r₁ in the 80–120 range). GPC, DSC, and Crystaf data for ethylene/1‐hexene copolymers of different compositions produced with the catalysts show that the reaction products have broad molecular weight and compositional distributions. A combination of kinetic data and structural data for the copolymers provided detailed information about the frequency of chain transfer reactions for several types of active centers present in the catalysts, their copolymerization efficiency, and stability. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5315–5329, 2008     

A New Route to Vitamin E Key‐Intermediates by Olefin Cross‐Metathesis

Ru‐Catalyzed olefin cross‐metathesis (CM) has been successfully applied to the synthesis of several phytyl derivatives ( 2b, 2d – f, 3b ) with a trisubstituted C?C bond, as useful intermediates for an alternative route to α‐tocopheryl acetate (vitamin E acetate; 1b ) (Scheme 1). Using the second‐generation Grubbs catalyst RuCl₂(C₂₁H₂₆N₂)(CHPh)PCy₃ (Cy = cyclohexyl; 4a ) and Hoveyda–Grubbs catalyst RuCl₂(C₂₁H₂₆N₂){CH‐C₆H₄(O‐ⁱPr)‐2} ( 4b ), the reactions were performed with various C‐allyl ( 5a – f, 7a,b ) and O‐allyl ( 8a – d ) derivatives of trimethylhydroquinone‐1‐acetate as substrates. 2,6,10,14‐Tetramethylpentadec‐1‐ene ( 6a ) and derivatives 6c – e of phytol ( 6b ) as well as phytal ( 6f ) were employed as olefin partners for the CM reactions (Schemes 2 and 5). The vitamin E precursors could be prepared in up to 83% isolated yield as (E/Z)‐mixtures.     

Maximizing the Catalytic Activity of Nanoparticles through Monolayer Assembly on Nitrogen‐Doped Graphene

We report a facile method for assembly of a monolayer array of nitrogen‐doped graphene (NG) and nanoparticles (NPs) and the subsequent transfer of two layers onto a solid substrate (S). Using 3 nm NiPd NPs as an example, we demonstrate that NiPd‐NG‐Si (Si=silicon wafer) can function as a catalyst and show maximum NiPd catalysis for the hydrolysis of ammonia borane (H₃NBH₃, AB) with a turnover frequency (TOF) of 4896.8 h^?1 and an activation energy (E_a) of 18.8 kJ mol^?1. The NiPd‐NG‐S catalyst is also highly active for catalyzing the transfer hydrogenation from AB to nitro compounds, leading to the green synthesis of quinazolines in water. Our assembly method can be extended to other graphene and NP catalyst materials, providing a new 2D NP catalyst platform for catalyzing multiple reactions in one pot with maximum efficiency.     

A 1,2,4‐diazaphospholane complex of rhodium

The crystal structure of a prospective olefin catalyst, namely {2‐[1‐acetyl‐5‐(2‐hydroxy­phenyl)‐4‐phenyl‐1,2,4‐di­aza­phospholan‐3‐yl]­phenyl acetate‐κP}chloro­(η⁴‐cyclo­octa‐1,5‐diene)rhodium(I) di­chloro­methane solvate, [RhCl(C₈H₁₂)(C₂₄H₂₃N₂O₄P)]·CH₂Cl₂, has been determined at 173 K. The five‐membered heterocycle of the phosphine ligand is in a slightly distorted twist conformation. An intramolecular N1—H1⃛Cl1 hydrogen bond contributes to the adopted conformation and may additionally participate in secondary interactions with substrates during catalysis.     

Ring‐Closing Metathesis Reactions: Interpretation of Conversion–Time Data

Conversion–time data were recorded for various ring‐closing metathesis (RCM) reactions that lead to five‐ or six‐membered cyclic olefins by using different precatalysts of the Hoveyda type. Slowly activated precatalysts were found to produce more RCM product than rapidly activated complexes, but this comes at the price of slower product formation. A kinetic model for the analysis of the conversion–time data was derived, which is based on the conversion of the precatalyst (Pcat) into the active species (Acat), with the rate constant k_act, followed by two parallel reactions: 1) the catalytic reaction, which utilizes Acat to convert reactants into products, with the rate k_cat, and 2) the conversion of Acat into the inactive species (Dcat), with the rate k_dec. The calculations employ two experimental parameters: the concentration of the substrate (c(S)) at a given time and the rate of substrate conversion (?dc(S)/dt). This provides a direct measure of the concentration of Acat and enables the calculation of the pseudo‐first‐order rate constants k_act, k_cat, and k_dec and of k_S (for the RCM conversion of the respective substrate by Acat). Most of the RCM reactions studied with different precatalysts are characterized by fast k_cat rates and by the k_dec value being greater than the k_act value, which leads to quasistationarity for Acat. The active species formed during the activation step was shown to be the same, regardless of the nature of different Pcats. The decomposition of Acat occurs along two parallel pathways, a unimolecular (or pseudo‐first‐order) reaction and a bimolecular reaction involving two ruthenium complexes. Electron‐deficient precatalysts display higher rates of catalyst deactivation than their electron‐rich relatives. Slowly initiating Pcats act as a reservoir, by generating small stationary concentrations of Acat. Based on this, it can be understood why the use of different precatalysts results in different substrate conversions in olefin metathesis reactions.     

碳化对超细Fe-Mn催化剂CO加氢反应行为的影响

以超细Fe-Mn催化剂为前驱体,对其进行了CH₄/H₂气氛下的高温碳化及反应行为研究。结果表明,高温碳化后,催化剂比表面积明显降低,主要物相结构为FeO-MnO尖晶石和α-Fe相,并有大量碳化铁微晶生成。在CO加氢反应中,碳化过程明显提高了烯烃选择性,降低了CH₄选择性,促进了链增长。结果认为,碳化过程改变了催化剂表面化学性质,增强了表面碱性,抑制了二次加氢反应,提高了烯烃选择性。     

Selective Transformation of Syngas into Gasoline‐Range Hydrocarbons over Mesoporous H‐ZSM‐5‐Supported Cobalt Nanoparticles

Bifunctional Fischer–Tropsch (FT) catalysts that couple uniform‐sized Co nanoparticles for CO hydrogenation and mesoporous zeolites for hydrocracking/isomerization reactions were found to be promising for the direct production of gasoline‐range (C_5–11) hydrocarbons from syngas. The Brønsted acidity results in hydrocracking/isomerization of the heavier hydrocarbons formed on Co nanoparticles, while the mesoporosity contributes to suppressing the formation of lighter (C_1–4) hydrocarbons. The selectivity for C_5–11 hydrocarbons could reach about 70 % with a ratio of isoparaffins to n‐paraffins of approximately 2.3 over this catalyst, and the former is markedly higher than the maximum value (ca. 45 %) expected from the Anderson–Schulz–Flory distribution. By using n‐hexadecane as a model compound, it was clarified that both the acidity and mesoporosity play key roles in controlling the hydrocracking reactions and thus contribute to the improved product selectivity in FT synthesis.     

Synthesis and Evaluation of Ruthenium 2‐Alkyl‐6‐mercaptophenolate Catalysts for Olefin Metathesis

A series of ruthenium carbene catalysts containing 2‐sulfidophenolate bidentate ligand with an ortho‐substituent next to the oxygen atom were synthesized. The molecular structure of ruthenium carbene complex containing 2‐isopropyl‐6‐sulfidophenolate ligand was confirmed through single crystal X‐ray diffraction. An oxygen atom can be found in the opposite position of the N‐heterocyclic carbene (NHC) based on the steric hindrance and strong trans‐effects of the NHC ligand. The ruthenium carbene catalyst can catalyze ring‐opening metathesis polymerization (ROMP) reaction of norbornene with high activity and Z‐selectivity and cross metathesis (CM) reactions of terminal alkenes with (Z)‐but‐2‐ene‐1,4‐diol to give Z‐olefin products (Z/E ratios, 70:30–89:11) in low yields (13%–38%). When AlCl₃ was added into the CM reactions, yields (51%–88%) were considerably improved and process becomes highly selective for E‐olefin products (E/Z ratios, 79:21–96:4). Similar to other ruthenium carbene catalysts, these new complexes can tolerate different functional groups.     

Intermediate Product Regulation in Tandem Solid Catalysts with Multimodal Porosity for High‐Yield Synthetic Fuel Production

Tandem catalysis is an attractive strategy to intensify chemical technologies. However, simultaneous control over the individual and concerted catalyst performances poses a challenge. We demonstrate that enhanced pore transport within a Co/Al₂O₃ Fischer–Tropsch (FT) catalyst with hierarchical porosity enables its tandem integration with a Pt/ZSM‐5 zeolitic hydrotreating catalyst in a spatially distant fashion that allows for catalyst‐specific temperature adjustment. Nevertheless, this system resembles the case of close active‐site proximity by mitigating secondary reactions of primary FT α‐olefin products. This approach enables the combination of in situ dewaxing with a minimum production of gaseous hydrocarbons (18 wt %) and an up to twofold higher (50 wt %) selectivity to middle distillates compared to tandem pairs based on benchmark mesoporous FT catalysts. An overall 80 % selectivity to liquid hydrocarbons from syngas is attained in one step, attesting to the potential of this strategy for increasing the carbon efficiency in intensified gas‐to‐liquid technologies.     

Dry Reforming of Methane on a Highly‐Active Ni‐CeO2 Catalyst: Effects of Metal‐Support Interactions on C−H Bond Breaking

Ni‐CeO₂ is a highly efficient, stable and non‐expensive catalyst for methane dry reforming at relative low temperatures (700 K). The active phase of the catalyst consists of small nanoparticles of nickel dispersed on partially reduced ceria. Experiments of ambient pressure XPS indicate that methane dissociates on Ni/CeO₂ at temperatures as low as 300 K, generating CH_x and CO_x species on the surface of the catalyst. Strong metal–support interactions activate Ni for the dissociation of methane. The results of density‐functional calculations show a drop in the effective barrier for methane activation from 0.9 eV on Ni(111) to only 0.15 eV on Ni/CeO_2?x(111). At 700 K, under methane dry reforming conditions, no signals for adsorbed CH_x or C species are detected in the C 1s XPS region. The reforming of methane proceeds in a clean and efficient way.