Synthesis of N-Heterocyclic Carbine Silver(Ⅰ)and Palladium(Ⅱ)Complexes with Acylated Piperazine Linker and Catalytic Activity in Three Types of C-C Coupling Reactions

Main observation and conclusion Two bis-imidazolium salts LH_(2)·Cl_(2) and LH_(2)·(PF_(6))_(2) with acylated piperazine linker and two N-heterocyclic carbene(NHC)silver(Ⅰ)and palladium(Ⅱ)complexes[L_(2)Ag_(2)](PF_(6))_(2)(1)and[L_(2)Pd_(2)Cl_(4)](2)were prepared.The crystal structures of LH_(2)·Cl_(2) and 1 were confirmed by X-ray analysis.In 1,one 26-membered macrometallocycle was generated through two silver(Ⅰ)ions and two bidentate ligands L.The catalytic activity of 2 was investigated in Sonogashira,Heck-Mizoroki and Suzuki-Miyaura reactions.The results displayed that these C-C coupling reactions can be smoothly carried out under the catalysis of 2.

N-heterocyclic carbene as a promising metal-free electrocatalyst with high efficiency for nitrogen reduction to ammonia

Electrocatalytic nitrogen reduction reaction(NRR)at ambient conditions holds great promise for sustainably synthesizing ammonia(NH3),while developing highly-efficient,long-term stable,and inexpensive catalysts to activate the inert N≡N bond is a key scientific issue.In this work,on the basis of the concept"N-heterocyclic carbenes(NHCs)",we propose a carbon decorated graphitic-carbon nitride(C/g-C3N4)as novel metal-free NRR electrocatalyst by means of density functional theory(DFT)computations.Our results reveal that the introduced C atom in g-C3N4 surface can be regarded as NHCs and catalytic sites for activating N≡N bond,and are stabilized by the g-C3N4 substrate due to sterically disfavored dimerization.Especially,this NHCs-based heterogeneous catalysis can efficiently reduce the activated N2 molecule to NH3 with a low overpotential of 0.05 V via an enzymatic mechanism.Our work is the first report of NHCs-based electrocatalyst for N2 fixation,thus opening an alternative avenue for advancing sustainable NH3 production.

Recent advances in heterogeneous catalytic hydrogenation and dehydrogenation of N-heterocycles

The selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines(py-THQ) and its derivatives has attracted a considerable amount of attention as they show great versatility in many pharmaceuticals, agrochemicals, and fine chemicals. Over the past few decades, great breakthroughs have been achieved in the controlled synthesis of efficient heterogeneous catalysts used for the selective hydrogenation of functionalized quinoline compounds, which allow one to correlate the structure-property relationships. In this review, we will summarize the recent significant progress achieved in this field covering the synthetic strategies, microstructural and chemical features, catalytic performance, and internal relationships. State-of-the-art noble metal-based single(Pd, Pt, Ru, Rh, Ir and Au) and bi/multi-metallic catalysts(RuCu, AuPd, and PdNi) are first introduced, followed by a summary of earth-abundant metal-based catalysts(Co, Fe, Ni, and Cu). Finally, the dehydrogenation of N-heterocycles is introduced to form a reversible hydrogenation/dehydrogenation system for H2 storage, which can be employed in a liquid organic hydrogen system. Furthermore, the reaction mechanism and future research direction in these areas are also discussed. This review will deepen our understanding of the catalytic transformation of N-heterocycles and provide guidance for researchers on the rational design of catalysts.

N-Heterocyclic carbene-catalyzed enantioselective(dynamic) kinetic resolutions and desymmetrizations

N-heterocyclic carbene-catalyzed enantioselective kinetic resolutions,dynamic kinetic resolutions,and desymmetrization reactions are systematically reviewed.The content is organized according to the activation modes involved in these transformations.Future advances within this highly active research field are discussed from our perspectives on the topic.

Chemoselective Transfer Hydrogenation of Nitroarenes with Ammonia Borane Catalyzed by Copper N-Heterocyclic Carbene Complexes

Herein,we present a method for the homogeneous hydrogenation of nitroarenes to produce anilines using low catalyst loading(1 mo%)of copper N-heterocyclic carbene complexes as the catalyst and ammonia borane as the source of hydrogen.A wide range of nitroarenes,featuring diverse functional groups,were selectively transformed into their corresponding primary aromatic amines with high yields.This process can be readily scaled up and exhibits compatibility with various sensitive functional groups,including halogen,trifluoromethyl,aminomethyl,alkenyl,cyano,ester,amide,and hydroxyl.Notably,this catalytic methodology finds application in the synthesis of essential drug compounds.Mechanistic investigations suggest that the in-situ-generated Cu-H species may serve as active intermediates,with reduction pathways involving species such as azobenzene,1,2-diphenylhydrazine,nitrosobenzene,and N-phenylhydroxylamine.

Recent advances in the synthesis and application of N-heterocyclic carbene-based molecular cages

N-Heterocyclic carbene(NHC)-based cages have emerged as a prominent and dynamic research area within the research field of chemistry. Leveraging the distinctive electronic and steric properties of NHC ligands, the design, synthesis, and application of these corresponding cages have garnered substantial scholarly interest. In recent years, we have witnessed the successful fabrication of diverse NHC-based cages through a range of synthetic methodologies, which hold significant potential for applications in molecular recognition and catalysis. In this review, we delve into the foundational synthetic strategies that underlie the creation of NHC-based cages, employing approaches encompassing metal–NHC chelation, coordination assembly,and covalent bonding. Additionally, we compile the diverse applications of these cages within catalytic processes and molecular recognition. Lastly, we shed light on the current limitations of synthesis and outline future trends in the development of NHCbased cages.

SOMO-HOMO level conversion in triarylmethyl-cored N-heterocyclic carbene-Au(I)complexes triggered by selecting coordination halogens

Conventionally,organic radicals adhere to the Aufbau principle,the energy level of the singly occupied molecular orbital(SOMO)is not below the highest occupied molecular orbital(HOMO),but somewhat abnormal phenomena have appeared recently.In this study,we introduce a novel strategy by incorporating unique NHC-Au-X units into a tris(2,4,6-trichlorophenyl)methyl(TTM)system to create metal-involved open-shell complexes,denoted as TTM-NHC-Au-X(X=I,Br,or Cl).Density-functional theory calculations were used to predict an inversion in the energy of the SOMO and highest doubly occupied molecular orbital(HOMO)of TTM-NHC-Au-I,which is supported by experimental results.Organometallic radicals TTM-NHC-Au-X demonstrated distinct properties with different coordinated halides.The radical behaviors have been investigated by EPR,UV-vis spectroscopy and cyclic voltammetry,additional structural information provided by structurally comparing related the precursor complexes given by X-ray crystallography.TTM-NHC-Au-I with SOMO-HOMO conversion(SHC)features a highly thermal decomposition temperature up to 305℃.Furthermore,the photostability of TTM-NHC-Au-I was found to be 75and 23 times greater than that of TTM-NHC-Au-Br and TTM-NHC-Au-Cl,respectively.These findings provide valuable insights into the structural and electronic design principles governing the occurrence of SOMO-HOMO conversion in open-shell systems.

Vanadium(V) Complexes Containing Unsymmetrical N-Heterocyclic Carbene Ligands: Highly Efficient Synthesis and Catalytic Behavior towards Ethylene/Propylene Copolymerization

The highly efficient method has been developed for the synthesis of NHC·VOCl_(3) containing symmetrical or unsymmetrical Nheterocyclic carbene(NHC) ligands by the transmetallation reaction of NHC·AgCl with VOCl_(3).The total isolated yield of VOCl_(3)[1,3-(2,4,6-Me_(3)C_(6)H_(2))_(2)(NCH=)_(2)C:](V4') reached 86% by transmetallation reaction,which is much higher than that(48%) by direct coordination method.This methodology has also been used to synthesize the novel vanadium complexes containing unsymmetrical NHC ligands of VOCl_(3)[PhCH_(2)NCH=CHNR)C:](V5',R=2,4,6-Me_(3)C_(6)H_(2);V6',R=2,4-Me_(2)-6-Ph-C_(6)H_(2);V7',R=2,6-^(i)Pr_(2)-C_(6)H_(3)) with high yield,which could not be obtained by direct coordination method.The catalytic activity and copolymerization ability would be improved by introducing unsymmetrical NHC ligands due to their less steric bulky effect.The vanadium complex V5' containing unsymmetrical NHC ligand exhibits higher catalytic activity(3.7×10^(5)g_(copolymer)·mol^(-1) of V·h^(-1)) than that of V4' containing symmetrical NHC ligand.Moreover,the higher propylene incorporation ratio(45.6 mol%) in the copolymers of ethylene with propylene could be obtained by using V5' than that(39.9%) by using V4'.The results would provide a highly efficient strategy for the synthesis of early transition metal complexes containing versitile NHC ligands,affording the catalyst with both high catalytic activity and copolymerization ability for the synthesis of high performance polyolefin elastomers.

Enantioselective Alkylation of Aldehydes with Organoborons Enabled by Nickel/N-Heterocyclic Carbene Catalysis

Transition-metal-catalyzed asymmetric alkylation of aldehydes represents a straightforward strategy for the synthesis of chiral secondary alcohols.However,efficient methods using organoborons as coupling reagents are rare.Herein,we report a highly enantioselective nickel-catalyzed alkylation reaction of aldehydes,using readily available alkylborons as nucleophiles.A wide variety of chiral secondary alcohols were prepared from commercially available aldehydes with high yields.The key to the excellent enantioselectivity and chemoselectivity was the employment of a bulky C2-symmetric chiral NHC ligand.This protocol features excellent enantiocontrol,mild conditions,and good functional group compatibility.

Operationally Simple Enantioselective Silane Reduction of Ketones by the [Ir(OMe)(cod)]2/Azolium Catalytic System

An operationally simple protocol was designed for the enantioselective silane reduction (ESR) of ketones using air- and moisture-stable [Ir(OMe)(cod)]2 (cod = 1,5-cyclooctadiene) (3) as a metal catalyst precursor. This reaction was driven by chiral hydroxyamide-functionalized azolium salt 2. The catalytic ESR reaction could be performed under benchtop conditions at room temperature. Treatment of 2 with 3 in THF yielded the monodentate IrCl(NHC)(cod) (NHC = N-heterocyclic carbene) complex 4 in 93% yield, herein the anionic methoxy ligand of 3 serves as an internal base that deprotonates the azolium ring of 2. The well-defined Ir complex 4 catalyzed the ESR reaction of propiophenone (6) with (EtO)2MeSiH using the pre-mixing reaction procedure. Based on this success, the catalytic ESR reaction was designed and implemented using an in situ-generated NHC/Ir catalyst derived from 2 and 3. Thus, a wide variety of aryl ketones could be reduced to the corresponding optically active alcohols in moderate to excellent stereoselectivities at room temperature without temperature control. Since the high catalytic activity of 3 was observed, we next evaluated several other transition metal catalyst precursors for the catalytic ESR reaction under the influence of 2. This evaluation revealed that Ir(acac)(cod) (acac = acetylacetonate) (28) and [IrCl(cod)]2 (5) can be successfully used as metal catalyst precursors in the ESR reaction.

桥联杂环卡宾前体[CH_3CH(NCHCHN)CH_2]_2Br_2^-的合成

甲基咪唑与1,2-二溴乙烷在THF(四氢呋喃)中以2∶1(摩尔比)反应合成了一种新型桥联氮杂环卡宾前体[CH3CH(NCHCHN)CH2]2Br2-,产物通过核磁和X射线衍射表征.晶体结构显示其晶体属单斜晶系P21/c,a=0.8475(3)nm,b=0.8916(3)nm,c=0.9234(3)nm,α=90°,β=108.214°,γ=90°,V=0.6628(4)nm3,Z=2,Dc=1.764 mg/m3,μ=6.097 mm-1,F(000)=348.产物分子结构中存在的大量氢键是其形成空间网状结构的主要原因.

β型线型碳及其应用研究

The transformation of β-carbine to diamond was studied by FTIR and XRD.The results indicated that the transformation was achieved with the pressure of 0.45MPa and temperature of 400 ℃.In the process,catalyst and diamond-crystal seeds were needless.

新型N-杂环卡宾咪唑盐的合成、表征与抑菌活性研究

以喹哪啶作为桥联基团,合成了五个新型N-杂环卡宾咪唑六氟磷酸盐化合物(5a^5e),其结构经1H NMR,13C NMR表征,用X-ray单晶衍射确定5b、5c和5e的晶体结构。单晶结构分析表明,晶体5b和5c均为三斜晶系、■空间群;5e晶体为单斜晶系、Cc空间群。5b的晶胞参数:a=6.945 1(10)nm,b=12.016 6(18) nm,c=14.791(2) nm,α=91.997(11)°,β=95.340(12)°,γ=105.845(8)°;5c的晶胞参数:a=9.975(3) nm,b=11.056(4) nm,c=12.382(4) nm,α=99.010(4)°,β=103.527(3)°,γ=112.734(3)°;5e的晶胞参数:a=18.058 9(18) nm,b=12.510 0(9) nm,c=13.365 9(12) nm,α=90.00°,β=124.522(7)°,γ=90.00°。抑菌实验结果表明,5a^5e对金黄色葡萄球菌和大肠杆菌有一定的抑制作用。

DL-SW微舱设计及对人造板VOCs的快速检测

为了缩短人造板挥发性有机化合物(VOCs)的检测周期,降低检测成本,提高产品的环保水平,设计出新型DL-SW微舱。以中密度纤维板、胶合板及刨花板为研究对象,在设定条件下对3种板材释放的VOCs进行快速检测,利用气相色谱-质谱联用仪(GC-MS)分析VOCs的具体成分及各组分含量,对比分析DL-SW微舱法与气候箱法的相关性。结果表明:DL-SW微舱法测得第1~3天3种板材总挥发性有机化合物(TVOC)释放量下降最快,最终均在14 d内达到稳定状态。测得3种板材释放VOCs的主要成分为芳香烃、烯烃及烷烃,占TVOCs总量50%以上,其次为醛类、醇类、酯类和酮类。高温和高相对湿度环境下,3种板材TVOC释放量有显著增加,中密度纤维板、胶合板、刨花板TVOC初始释放量分别为970.56,3 954.49和658.00μg/m^3。DL-SW微舱法与1 m^3气候箱法测得的3种板材释放的VOCs物质种类相同,TVOC释放趋势一致,达到稳定状态时TVOC浓度相对偏差分别为13.95%,11.04%和9.06%。测得的TVOC稳态释放量拟合得到公式y=0.877 5x+0.344 7,拟合度R^2为0.996。DL-SW微舱法较1 m^3气候箱法检测时间缩短50%以上,且成本低、可靠性强,能同时调节温湿度及空气交换率,可作为1 m^3气候箱的比对产品,有助于提高人造板产品的环保水平。

短碳纤维增强聚芳醚酮复合材料的断裂机理

利用扫描电子显微镜（ＳＥＭ）观察了短碳纤维增强聚芳醚酮复合材料（ＳＣＦ／ ＰＥＫ－Ｃ）在拉伸及冲击破坏条件下的断面形态，利用材料力学试验机测定ＳＣＦ／ＰＥＫ－Ｃ的应力－应变曲线，进而讨论了短碳纤维／聚芳醚酮复合材料的断裂机理。结果表明：此复合材料的微现破坏机理具有多样性。

负载型路易斯酸-超强碱双功能催化剂作用下的碳酸二甲酯直接合成

利用浸渍-焙烧法制备了负载型路易斯酸-超强碱双功能催化剂,并使用其一步直接由二氧化碳、甲醇和环氧丙烷合成碳酸二甲酯,并研究了催化剂负载量、反应的温度和时间、原料配比对反应结果的影响。指出了催化反应的机理,实验结果还显示焙烧对催化剂的超强碱活性位的形成有关键作用。

DMC合成反应器的腐蚀及选材研究

对多种合金在碳酸二甲酯(DMC)合成反应体系中的腐蚀进行了实验研究,为DMC合成反应器选材提供了实验依据。结果表明,合成反应的介质腐蚀性很强,合金材料腐蚀严重;在不影响催化剂活性和合成反应前提下,向反应体系中投加合适的添加剂可以有效地降低材料的腐蚀。

电石渣浆在大型火电机组烟气脱硫中的成功应用

介绍了太原第一热电厂利用太化集团氯碱分公司废电石渣浆在大型发电机组上进行烟气脱硫的试验情况,并对电石渣脱硫的可行性、经济性进行了分析,提出了电石渣综合利用的循环经济模式。

提高团结沟金矿选矿回收率的试验研究

通过对团结沟金矿原矿矿石性质、浮选尾矿、浮选精矿及浮选精矿浸渣特性的分析 ,对浮选精矿浸渣采用溜槽重选进行工业生产 ,溜槽重选精矿采用焙烧 -CIL炭浸法或微生物氧化法提金 ,溜槽重选尾矿再浮选 ;浮选精矿焙烧 ,焙砂CIL炭浸法提金进行了介绍。建议采用重选法回收浮选尾矿中的细粒级自然金、黄铁矿及赋存在黄铁矿与脉石矿物连生体中的金 。

鄂中地区下三叠统碳酸盐岩储层成岩作用与孔隙演化

鄂中沉湖一土地堂地区早三叠世以局限一半局限台地环境为主，有过短暂的台内浅滩环境，东部曾发展为蒸发台地环境．下三叠纯主要有微晶灰岩、微晶白云岩，夹少量亮晶颗粒灰岩，局部硬硬石膏岩；经历了海底环境的白云化，胶结、硬石膏化，大气环境的溶蚀，理藏环境的胶结、溶蚀、白云化、表生环境的溶蚀等成岩作用过程．大气及浅理藏环境产生的孔、缝隙多为后来的方解石等充填，对储层贡献甚微；深理藏环境的扩溶孔的形成及后期构造缝的产生与油气演化大致配套，具有一定的意义；表生环境的溶蚀孔隙，保存较好，对储层有较大贡献．区内下三叠统主要发育裂缝型及裂缝孔洞型两类储层，前者孔隙度低仅为２％～３％，后者孔隙度可达２６％左右，至今仍受大气淡水影响，保存条件差，不利于成藏．