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1.
《Angewandte Chemie (International ed. in English)》2017,56(42):13041-13046
Studies with a series of metal/ceria(111) (metal=Co, Ni, Cu; ceria=CeO2) surfaces indicate that metal–oxide interactions can play a very important role for the activation of methane and its reforming with CO2 at relatively low temperatures (600–700 K). Among the systems examined, Co/CeO2(111) exhibits the best performance and Cu/CeO2(111) has negligible activity. Experiments using ambient pressure X‐ray photoelectron spectroscopy indicate that methane dissociates on Co/CeO2(111) at temperatures as low as 300 K—generating CHx and COx species on the catalyst surface. The results of density functional calculations show a reduction in the methane activation barrier from 1.07 eV on Co(0001) to 0.87 eV on Co2+/CeO2(111), and to only 0.05 eV on Co0/CeO2−x (111). At 700 K, under methane dry reforming conditions, CO2 dissociates on the oxide surface and a catalytic cycle is established without coke deposition. A significant part of the CHx formed on the Co0/CeO2−x (111) catalyst recombines to yield ethane or ethylene. 相似文献
2.
In Situ and Theoretical Studies for the Dissociation of Water on an Active Ni/CeO2 Catalyst: Importance of Strong Metal–Support Interactions for the Cleavage of O–H Bonds
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Dr. Javier Carrasco Dr. David López‐Durán Dr. Zongyuan Liu Dr. Tomáš Duchoň Dr. Jaime Evans Dr. Sanjaya D. Senanayake Dr. Ethan J. Crumlin Prof. Dr. Vladimir Matolín Dr. José A. Rodríguez Dr. M. Verónica Ganduglia‐Pirovano 《Angewandte Chemie (International ed. in English)》2015,54(13):3917-3921
Water dissociation is crucial in many catalytic reactions on oxide‐supported transition‐metal catalysts. Supported by experimental and density‐functional theory results, the effect of the support on O? H bond cleavage activity is elucidated for nickel/ceria systems. Ambient‐pressure O 1s photoemission spectra at low Ni loadings on CeO2(111) reveal a substantially larger amount of OH groups as compared to the bare support. Computed activation energy barriers for water dissociation show an enhanced reactivity of Ni adatoms on CeO2(111) compared with pyramidal Ni4 particles with one Ni atom not in contact with the support, and extended Ni(111) surfaces. At the origin of this support effect is the ability of ceria to stabilize oxidized Ni2+ species by accommodating electrons in localized f‐states. The fast dissociation of water on Ni/CeO2 has a dramatic effect on the activity and stability of this system as a catalyst for the water‐gas shift and ethanol steam reforming reactions. 相似文献
3.
Activation of Methane and Ethane as Mediated by the Triatomic Anion HNbN−: Electronic Structure Similarity with a Pt Atom
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Dr. Jia‐Bi Ma Lin‐Lin Xu Qing‐Yu Liu Prof. Dr. Sheng‐Gui He 《Angewandte Chemie (International ed. in English)》2016,55(16):4947-4951
Investigations of the intrinsic properties of gas‐phase transition metal nitride (TMN) ions represent one approach to gain a fundamental understanding of the active sites of TMN catalysts, the activities and electronic structures of which are known to be comparable to those of noble metal catalysts. Herein, we investigate the structures and reactivities of the triatomic anions HNbN? by means of mass spectrometry and photoelectron imaging spectroscopy, in conjunction with density functional theory calculations. The HNbN? anions are capable of activating CH4 and C2H6 through oxidative addition, exhibiting similar reactivities to free Pt atoms. The similar electronic structures of HNbN? and Pt, especially the active orbitals, are responsible for this resemblance. Compared to the inert NbN?, the coordination of the H atom in HNbN? is indispensable. New insights into how to replace noble metals with TMNs may be derived from this combined experimental/computational study. 相似文献
4.
Qing‐Yu Liu Dr. Jia‐Bi Ma Dr. Zi‐Yu Li Chongyang Zhao Prof. Dr. Chuan‐Gang Ning Prof. Dr. Hui Chen Prof. Dr. Sheng‐Gui He 《Angewandte Chemie (International ed. in English)》2016,55(19):5760-5764
Atomic clusters are being actively studied for activation of methane, the most stable alkane molecule. While many cluster cations are very reactive with methane, the cluster anions are usually not very reactive, particularly for noble metal free anions. This study reports that the reactivity of molybdenum carbide cluster anions with methane can be much enhanced by adsorption of CO. The Mo2C2? is inert with CH4 while the CO addition product Mo2C3O? brings about dehydrogenation of CH4 under thermal collision conditions. The cluster structures and reactions are characterized by mass spectrometry, photoelectron spectroscopy, and quantum chemistry calculations, which demonstrate that the Mo2C3O? isomer with dissociated CO is reactive but the one with non‐dissociated CO is unreactive. The enhancement of cluster reactivity promoted by CO adsorption in this study is compared with those of reported systems of a few carbonyl complexes. 相似文献
5.
Mechanistic Insights into the Ni‐Catalyzed Reductive Carboxylation of C−O Bonds in Aromatic Esters with CO2: Understanding Remarkable Ligand and Traceless‐Directing‐Group Effects
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Yan‐Li Han Bing‐Yuan Zhao Kun‐Yao Jiang Hui‐Min Yan Dr. Zhu‐Xia Zhang Dr. Wen‐Jing Yang Prof. Dr. Zhen Guo Prof. Dr. Yan‐Rong Li 《化学:亚洲杂志》2018,13(12):1570-1581
The mechanism of the Ni0‐catalyzed reductive carboxylation reaction of C(sp2)?O and C(sp3)?O bonds in aromatic esters with CO2 to access valuable carboxylic acids was comprehensively studied by using DFT calculations. Computational results revealed that this transformation was composed of several key steps: C?O bond cleavage, reductive elimination, and/or CO2 insertion. Of these steps, C?O bond cleavage was found to be rate‐determining, and it occurred through either oxidative addition to form a NiII intermediate, or a radical pathway that involved a bimetallic species to generate two NiI species through homolytic dissociation of the C?O bond. DFT calculations revealed that the oxidative addition step was preferred in the reductive carboxylation reactions of C(sp2)?O and C(sp3)?O bonds in substrates with extended π systems. In contrast, oxidative addition was highly disfavored when traceless directing groups were involved in the reductive coupling of substrates without extended π systems. In such cases, the presence of traceless directing groups allowed for docking of a second Ni0 catalyst, and the reactions proceed through a bimetallic radical pathway, rather than through concerted oxidative addition, to afford two NiI species both kinetically and thermodynamically. These theoretical mechanistic insights into the reductive carboxylation reactions of C?O bonds were also employed to investigate several experimentally observed phenomena, including ligand‐dependent reactivity and site‐selectivity. 相似文献
6.
Dr. Jonas Baltrusaitis Prof. Dr. Coen de Graaf Prof. Dr. Ria Broer Prof. Dr. Eric V. Patterson 《Chemphyschem》2013,14(17):3960-3970
Sustainable, low‐temperature methods for natural gas activation are critical in addressing current and foreseeable energy and hydrocarbon feedstock needs. Large portions of natural gas resources are still too expensive to process due to their high content of hydrogen sulfide gas (H2S) mixed with methane, deemed altogether as sub‐quality or “sour” gas. We propose a unique method of activation to form a mixture of sulfur‐containing hydrocarbon intermediates, CH3SH and CH3SCH3, and an energy carrier such as H2. For this purpose, we investigated the H2S‐mediated methane activation to form a reactive CH3SH species by means of direct photolysis of sub‐quality natural gas. Photoexcitation of hydrogen sulfide in the CH4+H2S complex resulted in a barrierless relaxation by a conical intersection to form a ground‐state CH3SH+H2 complex. The resulting CH3SH could further be coupled over acidic catalysts to form higher hydrocarbons, and the resulting H2 used as a fuel. This process is very different from conventional thermal or radical‐based processes and can be driven photolytically at low temperatures, with enhanced control over the conditions currently used in industrial oxidative natural gas activation. Finally, the proposed process is CO2 neutral, as opposed to the current industrial steam methane reforming (SMR). 相似文献
7.
Prof. Laxmidhar Rout Dr. Bibhuti Bhusan Parida Dr. Jean‐Claude Florent Dr. Ludger Johannes Santosh Kumar Choudhury Dr. Ganngam Phaomei Prof. Joe Scanlon Dr. Emmanuel Bertounesque 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(42):14812-14815
C(sp)?H Bond activation of acetylene molecule still remains a challenge for synthetic organic chemists. In practice, acetylenes are activated by strong bases and metals. The first example for activating acetylenic protons under base and metal‐free conditions is reported here. It involves a general method for synthesizing propargylic derivatives of cotarnine. An array of tetrahydroisoquinolines alkaloids was synthesized by C(sp)?H bond activation of aromatic acetylenes with cotarnine at room temperature. A DFT‐based mechanism is proposed for the reaction. 相似文献
8.
采用密度泛函理论(DFT)计算了CH4在电中性(CeO2)m(m=1~3)团簇上的活化情况, 并对其机理进行了探讨. 计算结果表明, 甲烷C—H键在团簇上的活化为亲核加成模式, 电子由团簇流向甲烷C—H反键轨道, 使甲烷C—H键削弱而得以活化, 反应的过渡态为四中心结构. 团簇的桥氧位活化甲烷C—H键的活性大于端氧位, 而三重桥氧位的活性高于二重桥氧位. 团簇中作用位点Ce和O原子的电荷布居与其活化甲烷C—H的能力密切相关. 溶剂的存在不仅降低了甲烷C—H活化自由能垒, 而且使与甲烷作用的团簇各位点的活性差异缩小. 相似文献
9.
Burney C Carmichael D Forissier K Green JC Mathey F Ricard L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5381-5390
The reaction of the bulky phospholide salt Li(2,5-tBu2PC4H2) x 2THF (1; THF = tetrahydrofuran) with [NiCp*(acac)] (HCp* = pentamethylcyclopentadiene, Hacac = acetylacetone) gives the green air-sensitive phosphanickelocene [NiCp*(2,5-tBu2PC4H2)] (2) in yields of about 85%. An X-ray structural determination of 2 shows long Ni-ring bonds and "delocalised" ring P-C and C-C bonds characteristic of a classical 20-valence-electron (ve) nickelocene. The electronic structure of 2 has been clarified through a combined Amsterdam density functional (ADF) and photoelectron spectroscopic study, which indicates that the higher lying semi-occupied molecular orbital (SOMO) (-5.82 eV) has a' symmetry and that the phosphorus "lone pair" is energetically low-lying (-8.15 eV). Oxidation of phosphanickelocene 2 by AgBF4 occurs quantitatively to give the corresponding air-sensitive orange phosphanickelocenium salt [NiCp*(2,5-tBu2PC4H2)][BF4] (3). This complex has also been characterised by an X-ray crystallographic study, which reveals long Ni-C(alpha) and short C(alpha)-C(beta) bonds in the phospholyl ligand indicative of a SOMO having a' symmetry. PMe3 reacts with 2 at room temperature to provoke a ring-slip reaction that gives the 18ve complex [NiCp*eta1-(2,5-tBu2PC4H2)(PMe3)] (4), but shows no reaction with the phosphanickelocenium salt 3 under the same conditions. 相似文献
10.
Inserting CO2 into Aryl C−H Bonds of Metal–Organic Frameworks: CO2 Utilization for Direct Heterogeneous C−H Activation
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Wen‐Yang Gao Haifan Wu Kunyue Leng Prof. Yinyong Sun Prof. Shengqian Ma 《Angewandte Chemie (International ed. in English)》2016,55(18):5472-5476
Described for the first time is that carbon dioxide (CO2) can be successfully inserted into aryl C?H bonds of the backbone of a metal–organic framework (MOF) to generate free carboxylate groups, which serve as Brønsted acid sites for efficiently catalyzing the methanolysis of epoxides. The work delineates the very first example of utilizing CO2 for heterogeneous C?H activation and carboxylation reactions on MOFs, and opens a new avenue for CO2 chemical transformations under mild reaction conditions. 相似文献
11.
Dipl.‐Chem. Max Amende Stefan Schernich Dr. Marek Sobota Ioannis Nikiforidis Priv.‐Doz. Dr. Wolfgang Hieringer Dr. Daniel Assenbaum Dipl.‐Ing. Christoph Gleichweit Dipl.‐Chem. Hans‐Jörg Drescher Dr. Christian Papp Prof. Dr. Hans‐Peter Steinrück Prof. Dr. Andreas Görling Prof. Dr. Peter Wasserscheid Dr. Mathias Laurin Prof. Dr. Jörg Libuda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):10854-10865
Dodecahydro‐N‐ethylcarbazole (H12‐NEC) has been proposed as a potential liquid organic hydrogen carrier (LOHC) for chemical energy storage, as it combines both favourable physicochemical and thermodynamic properties. The design of optimised dehydrogenation catalysts for LOHC technology requires a detailed understanding of the reaction pathways and the microkinetics. Here, we investigate the dehydrogenation mechanism of H12‐NEC on Pd(111) by using a surface‐science approach under ultrahigh vacuum conditions. By combining infrared reflection–absorption spectroscopy, density functional theory calculations and X‐ray photoelectron spectroscopy, surface intermediates and their stability are identified. We show that H12‐NEC adsorbs molecularly up to 173 K. Above this temperature (223 K), activation of C? H bonds is observed within the five‐membered ring. Rapid dehydrogenation occurs to octahydro‐N‐ethylcarbazole (H8‐NEC), which is identified as a stable surface intermediate at 223 K. Above 273 K, further dehydrogenation of H8‐NEC proceeds within the six‐membered rings. Starting from clean Pd(111), C? N bond scission, an undesired side reaction, is observed above 350 K. By complementing surface spectroscopy, we present a temperature‐programmed molecular beam experiment, which permits direct observation of dehydrogenation products in the gas phase during continuous dosing of the LOHC. We identify H8‐NEC as the main product desorbing from Pd(111). The onset temperature for H8‐NEC desorption is 330 K, the maximum reaction rate is reached around 550 K. The fact that preferential desorption of H8‐NEC is observed even above the temperature threshold for H8‐NEC dehydrogenation on the clean surface is attributed to the presence of surface dehydrogenation and decomposition products during continuous reactant exposure. 相似文献
12.
Distal Weak Coordination of Acetamides in Ruthenium(II)‐Catalyzed C−H Activation Processes
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Qingqing Bu Torben Rogge Dr. Vladislav Kotek Prof. Dr. Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2018,57(3):765-768
C?H activations with challenging arylacetamides were accomplished by versatile ruthenium(II) biscarboxylate catalysis. The distal C?H functionalization offers ample scope—including twofold oxidative C?H functionalizations and alkyne hydroarylations—through facile base‐assisted internal electrophilic‐type substitution (BIES) C?H ruthenation by weak O‐coordination. 相似文献
13.
14.
Dr. Shaoguang Zhang Dr. Haixia Li Dr. Aaron M. Appel Prof. Michael B. Hall Dr. R. Morris Bullock 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9493-9497
Unusual cleavage of P?C and C?H bonds of the P2N2 ligand, in heteroleptic [Ni(P2N2)(diphosphine)]2+ complexes under mild conditions, results in the formation of an iminium formyl nickelate featuring a C,P,P‐tridentate coordination mode. The structures of both the heteroleptic [Ni(P2N2)(diphosphine)]2+ complexes and the resulting iminium formyl nickelate have been characterized by NMR spectroscopy and single‐crystal X‐ray diffraction analysis. Density functional theory (DFT) calculations were employed to investigate the mechanism of the P?C/C?H bond cleavage, which involves C?H bond cleavage, hydride rotation, Ni?C/P?H bond formation, and P?C bond cleavage. 相似文献
15.
Dr. Lingbing Kong Dr. Rakesh Ganguly Dr. Yongxin Li Prof. Dr. Rei Kinjo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):1922-1925
Oxidative addition of the C?O bond in L2PhB: (L=oxazol‐2‐ylidene) to an AlI center induced ring expansion of an oxazol‐2‐ylidene ring, affording a unique organoboron species formally involving either an Al, N, O mixed heterocyclic carbene or anionic (amino)(boryl)carbene fragment. 相似文献
16.
Six density function theory methods (B3LYP, B3P86, MPWB1K1, MPWPW91, PBEPBE, TPSS1KCIS3) were used to calculate bond dissociation enthalpies of nitro compounds, where the B3P86 method was found to give the most accurate predictions. Using the B3P86 method meta‐ and para‐substituted nitroaromatics were systematically studied for the first time. The remote substituent effects, Hammett relationships, and the origin of the substituent effects were discussed on the basis of the calculated results. Both meta‐ and para‐substituted nitromethyl‐benzenes showed significant substituent effects and a fair correlation against substituent constants σp+ The ground state effects were found to play the major role in determining the overall substituent effects. Meanwhile, nitroamino‐ benzenes showed irregular substituent effects and a poorer Hammett correlation, where both ground and radical state effects contributed to the overall substituent effects. 相似文献
17.
Raphael M. Jay Sebastian Eckert Vinícius VazdaCruz Mattis Fondell Rolf Mitzner Alexander Fhlisch 《Angewandte Chemie (International ed. in English)》2019,58(31):10742-10746
Covalency is found to even out charge separation after photo‐oxidation of the metal center in the metal‐to‐ligand charge‐transfer state of an iron photosensitizer. The σ‐donation ability of the ligands compensates for the loss of iron 3d electronic charge, thereby upholding the initial metal charge density and preserving the local noble‐gas configuration. These findings are enabled through element‐specific and orbital‐selective time‐resolved X‐ray absorption spectroscopy at the iron L‐edge. Thus, valence orbital populations around the central metal are directly accessible. In conjunction with density functional theory we conclude that the picture of a localized charge‐separation is inadequate. However, the unpaired spin density provides a suitable representation of the electron–hole pair associated with the electron‐transfer process. 相似文献
18.
2‐Pyridone is a ubiquitous motif in natural products, drug molecules, ligands in catalysis and organic materials. There is a necessity of direct step‐economic methods for the construction of 2‐pyridone based molecules. Strategically, the primary developments have led to the C3‐functionalizations due to the inherent reactivity of this center. Despite this, many elegant transition metal‐catalysed methods have been established to introduce versatile functional groups at the C4, C5 and C6‐position via direct C?H bond functionalizations. This minireview focuses on the categorized introduction of different functional groups at the 2‐pyridone scaffolds beyond C3‐selectivity and discusses substrate scope, limitations and plausible mechanistic details. 相似文献
19.
本文利用G3B3 和CBS-Q高精度理论方法检验了一系列胺类有机化合物中α-碳氢键离解能的实验测量值,在此基础上筛选出(U)BHandH/6-311++G(2df, 2p)//(U)B3LYP/6-31G(d)方法,发现其可以准确快速的预测氮α-碳氢键离解能。运用该方法研究了若干含氮药物分子,发现氮α-碳氢键离解能随药物分子结构发生明显变化。为了阐明其变化规律,系统研究单取代和双取代基效应,并解释了不同取代基效应的来源。 相似文献
20.
《Angewandte Chemie (International ed. in English)》2017,56(42):12898-12902
The robust, high‐valent NiIV complex [(Py)2NiIVF2(CF3)2] (Py=pyridine) was synthesized and fully characterized by NMR spectroscopy, X‐ray diffraction, and elemental analysis. It reacts with aromatic compounds at 25 °C to form the corresponding benzotrifluorides in nearly quantitative yield. The monomeric and dimeric NiIIICF3 complexes 2 ⋅Py and 2 were identified as key intermediates, and their structures were unambiguously determined by EPR spectroscopy and X‐ray diffraction. Preliminary kinetic studies in combination with the isolation of reaction intermediates confirmed that the C−H bond‐breaking/C−CF3 bond‐forming sequence can occur both at NiIVCF3 and NiIIICF3 centers. 相似文献