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.

Synthesis, Crystal Structure and Catalytic Behavior of 1-Ethyl-3-benyl-imidazolyl Tetranuclear N-Heterocyclic Carbene Silver Bromide

The title complex [Ag（carbene）2]2[Ag2Br4] has been synthesized by the reaction of Ag2O with 1-ethyl-3-benyl-imidazolium bromide in DMSO at room temperature, and characterized by elemental analysis, 1H NMR and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P with a = 10.1597（10）, b =11.0646（11）, c = 13.0245（14） , α = 102.230（2）, β = 90.606, γ = 113.9250（10）o, V = 1300.3（2） 3, Mr = 748.06, Z = 2, Dc = 1.911 g/cm3, μ（MoKα） = 4.60 mm-1 and F（000） = 728. The structure was refined to R = 0.0316 and wR = 0.0835 for 3744 observed reflections with I 〉 2σ（I）. The title compound crystallizes as a centrosymmetric tetranuclear compound. One half of the molecule comprises the asymmetric unit of the structure. The Ag（1） atom is nearly linear or T-shaped when the Ag（1）-Ag（2） interaction is taken into consideration, which is bi-coordinated by two carbene carbon atoms. The Ag（2） atom adopts tetrahedral geometry. The catalytic behavior of the title complex has been investigated, and the results indicate it has a highly catalytic activation for L-lactide polymerization.

Synthesis and Structural Study of a N-Heterocyclic Carbene Trinuclear Silver(Ⅰ)Complex

The bis-benzimidazolium salt bis[2-（N-ethylbenzimidazoliumyl）ethyl]amine hexafluorophosphate（LH2·（PF6）2） and its N-heterocyclic carbene silver（Ⅰ） complex[L2Ag3]（PF6）3（1）have been prepared and characterized.In complex 1,a trinuclear silver（Ⅰ） architecture is formed by two tridentate ligands and three silver（I） atoms,in which one 12- and two 7-membered rings are contained.In the crystal packing of 1,1D chain and 2D supramolecular layer are formed via intermolecular weak interactions,including π…π interactions and C-H…π contacts.Additionally,the fluorescence emission spectra of LH2-（PF6）2 and 1 are described.

Transformations of biomass-based levulinate ester into γ-valerolactone and pyrrolidones using carbon nanotubes-grafted N-heterocyclic carbene ruthenium complexes

As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,agrochemical,material industrial and other chemical production.In this research,we demonstrated transformations of biomass-based ethyl levulinate(EL)into GVL and pyrrolidones by using heterogeneous catalysts(CNT-Ru-1)with N-heterocyclic carbene ruthenium(NHC-Ru)complex grafted on multi-walled carbon nanotube(CNT).The Ru catalyst showed high efficiency on EL hydrogenation to GVL with both EL conversion and GVL yield exceeding 99%.Moreover,the Ru catalyst readily promoted reductive amination of EL in the presence of various amines for pyrrolidone synthesis.Finally,the Ru catalyst was also applicable to hydrogenation of various carbonyl compounds for the synthesis of the corresponding alcohols with excellent catalytic performance.The research provides insight for heterogenizing the homogeneous noble metal-based catalysts with high catalytic active for biomass-based transformations.

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.

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.

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.

An Ultralong Low-Temperature Phosphorescent Pentagonal-Prismatic Organometallic Cylinder Featuring Pentaphenylpyrrole-N-Heterocyclic Carbenes

A pentagonal-prismatic cylinder[Ag5(L)2](PF6)5 obtained from the pentaphenylpyrrole-bridged pentaimidazolium salt H5-L(PF6)5 and AgI ions was determined by X-ray diffraction analyses.The target organometallic cylinder not only exhibited enhanced fluorescence emission in dilute solution at room temperature but also showed an improved phosphorescence ratio compared with the free precursor and maintained a long lifetime(1.39 s)in the solid state at 77 K.Furthermore,the experimental results and DFT calculations confirmed that the formation of the organometallic cylinder promoted intersystem crossing.Meanwhile,the frontier orbitals of[Ag5(L)2](PF6)5 showed the main contribution of building block PPP as the luminescence source of[Ag5(L)2](PF6)5 by a modest heavy-atom effect.These results provide a strategy for constructing enhanced phosphorescent emission and long lifetime organometallic supramolecular phosphorescent materials.

N-Heterocyclic carbene catalyzed C-acylation reaction for access to linear aminoenones

An N-heterocyclic carbene(NHC)-catalyzed carbonyl nucleophilic substitution reaction between 1-cyclopropylcarbaldehydes and N-sulfonyl imines is developed for access to linearβ-aminoenone products.Theβ-aminoenones containing cyclopropyl fragments can be afforded in moderate to excellent yields under mild conditions.The reaction features excellent trans-diastereoselectivities and the desired aminoenone products are all afforded as Z-isomers.

N-heterocyclic carbene-catalyzed arene formation reactions

N-heterocyclic carbene-catalyzed reactions for the formation of aromatic compounds are reviewed.The reactions are subdivided into 4 types based on their activation modes.A brief summary on the achievements and the challenges remaining in Nheterocyclic carbene(NHC)-catalyzed arene construction processes is provided at the end of this review.An outlook into the future research direction within this field is also given based on our own opinion and knowledge on the trends of the development of NHC organocatalysis.

N-heterocyclic carbene-catalyzed radical reactions

While N-heterocyclic carbene(NHC)catalyzed electron-pair-transfer processes have been developed into an important tool for synthetically important bond formations during the past decades,the corresponding radical reactions via NHC catalysis have only received growing attention in the past six years.Taking into account the advantages NHC-catalyzed radical reactions might bring,such as creating new activation modes that were previously unobtainable,it is worthwhile to provide a conceptual understanding of this emerging area.Therefore,herein we give an overview of NHC-catalyzed radical reactions via different synthetic techniques.

Synthesis of a Dichlorosilaimine Coordinated by an N-Heterocyclic Carbene from ArN（SiMe3）SiHCl2

NHC-stabilized dichlorosilaimine ArN=Si（IiPr）Cl2 （2） （Ar=2,6-iPr2C6H3, IiPr=1,3-diisopropyl-4,5-dimeth- ylimidazol-2-ylidene） and disilane LSiHCl-SiCl2L （L=ArNSiMe3） （3） could be synthesized from the reaction of aminodichlorosilane ArN（SiMe3）SiHCl2 （1） with IiPr under different conditions. This represents the first route to the generation of donor-stabilized dichlorosilaimine from substituted chlorosilane in the presence of an NHC via dehydrosilylation.

N-Heterocyclic Carbene-Palladium Complex Catalyzed Oxidative Carbonylation of Amines to Ureas

Palladium carbene shows high efficiency without any promoter on oxidative carbonylation of amines to ureas and a new type of palladium carbene complex containing both an aniline and an NHC ligands was found to be the active species for the reaction.

Recent advances in N-heterocyclic carbene-catalyzed radical reactions

The N-heterocyclic carbene(NHC)-catalyzed reactions involving two-electron reaction pathway have been well-established.However,the development of NHC-catalyzed radical reactions is still in its infancy in terms of reaction types and enantioselectivity.In the past decade,several elegant NHC-catalyzed radical reactions have been developed,including NHC-catalyzed oxidation of aldehydes to esters,reductive coupling reactions using Breslow intermediate as SET reductant and NHC-catalyzed reactions via radical homoenolates,dienoaltes and trienolates.This review summarizes the recent advances in NHC-catalyzed reactions involving radical intermediates.

Stereoselective Ring-opening Polymerization of rac-Lactide by Bulky Chiral and Achiral N-heterocyclic Carbenes

Despite the extraordinary success has been achieved in metal catalyst-promoted stereoselective ring-opening polymerization（ROP） of rac-lactide（rac-LA）, well-controlled stereoselective rac-LA ROP by organic catalyst still remains a scientific challenge. Here we report our investigations into organocatalytic stereoselective ROP of rac-LA by utilizing novel bulky chiral and achiral N-heterocyclic carbenes（NHC）, 1,3-bis-（1′-naphthylethyl）imidazolin-2-ylidene. The effect of polymerization conditions（e.g. solvent, temperature, alcohol initiator） on ROP behavior by these bulky NHCs has been fully studied, leading to the formation of isotactic-rich stereoblock polylactide（Pi = 0.81） under optimized conditions with high activity（Conv. = 98% in 30 min） and narrow molecular weight dispersity（D = 1.05）.

Intermolecular Stetter reaction of aromatic aldehydes with(E)-(2-nitrovinyl)cyclohexane induced by N-heterocyclic carbene and thiourea

Intermolecular Stetter reaction of aromatic aldehydes with（E）-（2-nitrovinyl）cyclohexane catalyzed by thiazolium A has been developed.The reaction rate and efficiency are profoundly impacted by the presence of thiourea B.The reaction affords moderate to good yields of the Stetter product.Some factors influencing yield were discussed.

Direct C-H Bond Activation of Benzoxazole and Benzothiazole with Aryl Bromides Catalyzed by Palladium（Ⅱ）-N-heterocyclic Carbene Complexes

Herein, we report that a series of novel palladium（II）-NHC complexes （NHC=N-heterocyclic carbene） were synthesized. The structures of all novel complexes were characterized by ^1H NMR, ^13C NMR, FT-IR spectroscopy and elemental analysis techniques. These palladium（ll）-NHC complexes were tested as efficient catalysts in the direct C-H bond activation of benzoxazole and benzothiazole with aryl bromides in the presence of 1 mol% catalyst loading at 150 ℃ for 4 h. Under the given conditions, various aryl bromides were successfully applied as the arylating reagents to achieve the 2-arylbenzoxazoles and 2-arylbenzothiazoles in acceptable to high yields.

N-heterocyclic carbene-catalyzed atroposelective synthesis of axially chiral 5-aryl 2-pyrones from enals

Axially chiral molecules have been widely used in inorganic,material and medicinal chemistry.Compared with well-established N-heterocyclic carbene(NHC)-catalyzed asymmetric construction of centrally chiral molecules,NHC-catalyzed atroposelective synthesis of axially chiral molecules remains largely underdeveloped.Notably,alkynyl acyl azolium intermediates were commonly used in constructing a heteroaryl ring to furnish axially enantioenriched heteroaryl-aryls.The inherent character of the intermediates often led to react with sterically hindered substrates difficultly.Herein,we have successfully disclosed the atroposelective synthesis of axially chiral heteroaryl-aryls from sterically hindered enols through the use of chiral NHCs as catalysts for highly enantioselective Coates-Claisen rearrangements via catalytically generatedα,β-unsaturated acyl azoliums.This approach will enable the concise synthesis of valuable tetra-ortho-substituted 2-pyrones in one step with good yield and chirality control.

Assembly of versatile fluorine-containing structures via N-heterocyclic carbene organocatalysis

Owing to the unique properties of fluorine-containing moieties in the pharmaceuticals,agrochemicals and materials,several synthetic efforts(i.e.,enzymatic resolution,transition-metal catalysis,and organocatalysis)have been frequently made to fabricate these fluorinated structures.As powerful organic catalysts,N-heterocyclic carbenes can activate carbonyl group and realize the chiral intervention of multiple sites near the carbonyl group,and have an irreplaceable power to construct fluorine-containing fragments.However,NHC-related reviews focused on the versatile synthesis of fluorine-containing fragments are absolutely rare to this date.This mini-review highlights the invention of inserting fluorine atom or assembling fluorine-containing fragments via NHC organocatalysis.By summarizing the achievements in this field,we are eager to provide enlightening clues for further developments.

N-Heterocyclic carbene-catalyzed synthesis of acetyltributylcitrate via a transesterification reaction

A new methodology for the synthesis of a green plasticizer acetyltributylcitrate through a transesterification reaction was developed. Under the catalysis of alkyl-substituted imidazol-type N-heterocyclic carbenes, tributyl citrate can react with vinyl acetate smoothly to give ATBC in high yield.