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Artykuły w czasopismach na temat "Transition Metal-NHC Complexes"

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Winkelmann, Ole, Christian Näther i Ulrich Lüning. "Bimacrocyclic NHC transition metal complexes". Journal of Organometallic Chemistry 693, nr 6 (marzec 2008): 923–32. http://dx.doi.org/10.1016/j.jorganchem.2007.11.064.

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Yamaguchi, Yoshitaka. "Synthesis of Transition-metal NHC Complexes using “Protected” NHC Adduct". Bulletin of Japan Society of Coordination Chemistry 52 (2008): 43–54. http://dx.doi.org/10.4019/bjscc.52.43.

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Weiss, Daniel T., Philipp J. Altmann, Stefan Haslinger, Christian Jandl, Alexander Pöthig, Mirza Cokoja i Fritz E. Kühn. "Structural diversity of late transition metal complexes with flexible tetra-NHC ligands". Dalton Transactions 44, nr 42 (2015): 18329–39. http://dx.doi.org/10.1039/c5dt02386f.

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Yang, Shiyi, Tongliang Zhou, Xiang Yu i Michal Szostak. "Ag–NHC Complexes in the p-Activation of Alkynes". Molecules 28, nr 3 (18.01.2023): 950. http://dx.doi.org/10.3390/molecules28030950.

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Silver–NHC (NHC = N-heterocyclic carbene) complexes play a special role in the field of transition-metal complexes due to (1) their prominent biological activity, and (2) their critical role as transfer reagents for the synthesis of metal-NHC complexes by transmetalation. However, the application of silver–NHCs in catalysis is underdeveloped, particularly when compared to their group 11 counterparts, gold–NHCs (Au–NHC) and copper–NHCs (Cu–NHC). In this Special Issue on Featured Reviews in Organometallic Chemistry, we present a comprehensive overview of the application of silver–NHC complexes in the p-activation of alkynes. The functionalization of alkynes is one of the most important processes in chemistry, and it is at the bedrock of organic synthesis. Recent studies show the significant promise of silver–NHC complexes as unique and highly selective catalysts in this class of reactions. The review covers p-activation reactions catalyzed by Ag–NHCs since 2005 (the first example of p-activation in catalysis by Ag–NHCs) through December 2022. The review focuses on the structure of NHC ligands and p-functionalization methods, covering the following broadly defined topics: (1) intramolecular cyclizations; (2) CO2 fixation; and (3) hydrofunctionalization reactions. By discussing the role of Ag–NHC complexes in the p-functionalization of alkynes, the reader is provided with an overview of this important area of research and the role of Ag–NHCs to promote reactions that are beyond other group 11 metal–NHC complexes.
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Visbal, Renso, i M. Concepción Gimeno. "N-heterocyclic carbene metal complexes: photoluminescence and applications". Chem. Soc. Rev. 43, nr 10 (2014): 3551–74. http://dx.doi.org/10.1039/c3cs60466g.

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Neshat, Abdollah, Piero Mastrorilli i Ali Mousavizadeh Mobarakeh. "Recent Advances in Catalysis Involving Bidentate N-Heterocyclic Carbene Ligands". Molecules 27, nr 1 (24.12.2021): 95. http://dx.doi.org/10.3390/molecules27010095.

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Since the discovery of persistent carbenes by the isolation of 1,3-di-l-adamantylimidazol-2-ylidene by Arduengo and coworkers, we witnessed a fast growth in the design and applications of this class of ligands and their metal complexes. Modular synthesis and ease of electronic and steric adjustability made this class of sigma donors highly popular among chemists. While the nature of the metal-carbon bond in transition metal complexes bearing N-heterocyclic carbenes (NHCs) is predominantly considered to be neutral sigma or dative bonds, the strength of the bond is highly dependent on the energy match between the highest occupied molecular orbital (HOMO) of the NHC ligand and that of the metal ion. Because of their versatility, the coordination chemistry of NHC ligands with was explored with almost all transition metal ions. Other than the transition metals, NHCs are also capable of establishing a chemical bond with the main group elements. The advances in the catalytic applications of the NHC ligands linked with a second tether are discussed. For clarity, more frequently targeted catalytic reactions are considered first. Carbon–carbon coupling reactions, transfer hydrogenation of alkenes and carbonyl compounds, ketone hydrosilylation, and chiral catalysis are among highly popular reactions. Areas where the efficacy of the NHC based catalytic systems were explored to a lesser extent include CO2 reduction, C-H borylation, alkyl amination, and hydroamination reactions. Furthermore, the synthesis and applications of transition metal complexes are covered.
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Savchuk, Mariia, Lucas Bocquin, Muriel Albalat, Marion Jean, Nicolas Vanthuyne, Paola Nava, Stéphane Humbel, Damien Hérault i Hervé Clavier. "Transition metal complexes bearing atropisomeric saturated NHC ligands". Chirality 34, nr 1 (5.11.2021): 13–26. http://dx.doi.org/10.1002/chir.23378.

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Scattolin, Thomas, i Steven P. Nolan. "Synthetic Routes to Late Transition Metal–NHC Complexes". Trends in Chemistry 2, nr 8 (sierpień 2020): 721–36. http://dx.doi.org/10.1016/j.trechm.2020.06.001.

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Zhang, Dao, i Guofu Zi. "N-heterocyclic carbene (NHC) complexes of group 4 transition metals". Chemical Society Reviews 44, nr 7 (2015): 1898–921. http://dx.doi.org/10.1039/c4cs00441h.

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Messelberger, Julian, Annette Grünwald, Philipp Stegner, Laura Senft, Frank W. Heinemann i Dominik Munz. "Transmetalation from Magnesium–NHCs—Convenient Synthesis of Chelating π-Acidic NHC Complexes". Inorganics 7, nr 5 (22.05.2019): 65. http://dx.doi.org/10.3390/inorganics7050065.

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The synthesis of chelating N-heterocyclic carbene (NHC) complexes with considerable π-acceptor properties can be a challenging task. This is due to the dimerization of free carbene ligands, the moisture sensitivity of reaction intermediates or reagents, and challenges associated with the workup procedure. Herein, we report a general route using transmetalation from magnesium–NHCs. Notably, this route gives access to transition-metal complexes in quantitative conversion without the formation of byproducts. It therefore produces transition-metal complexes outperforming the conventional routes based on free or lithium-coordinated carbene, silver complexes, or in situ metalation in dimethyl sulfoxide (DMSO). We therefore propose transmetalation from magnesium–NHCs as a convenient and general route to obtain NHC complexes.
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Rozprawy doktorskie na temat "Transition Metal-NHC Complexes"

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Andrew, Rhiann E. "Late transition metal complexes of NHC-based macrocycles". Thesis, University of Warwick, 2016. http://wrap.warwick.ac.uk/85928/.

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N-heterocyclic carbene (NHC) ligands are an important and diverse ligand class, conferring stability and enabling reaction control of coordinated metal centres. Pincer ligand architectures bearing such donors are an increasingly prevalent design motif, combining the strong donor characteristics of carbenes with the favourable thermal stability possible with a mer-tridentate geometry. Macrocyclic variants of NHC-based pincers are of interest as they may impart further stability and reaction control, in addition to serving as potential building blocks for the construction of interlocked, supramolecular systems. Enabling study of the reactivity and structural properties of late transition metal complexes of macrocyclic CNC pincer ligands, the coordination chemistry of a series of pro-ligands of varying ring size (n = 1; m = 8, 10, 12) has been explored. Investigation of the dynamics and structures of palladium(II) halide complexes identified an optimal ring size, which was subsequently employed in the preparation of rhodium-based derivatives (n = 0, 1; m = 12) via two converging synthetic routes. The organometallic chemistry, dynamic behaviour and structures of the resulting rhodium complexes are described. Through investigation of terminal alkyne coupling reactions using a macrocyclic rhodium ethylene complex, potential for the preparation of novel supramolecular assemblies was explored. As a result, a series of complexes bearing mechanically entrapped enynes were isolated and fully characterised in solution and the solid-state.
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Berro, Patrick. "Exploring Photocatalytic and Electrocatalytic Reduction of CO2 with Re(I) and Zn(II) Complexes and Attempts to Employ a Novel Carbene Ligand to this Endeavor". Thesis, Université d'Ottawa / University of Ottawa, 2021. http://hdl.handle.net/10393/41625.

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With the blend of addressing issues of sustainable energy with the environmental worries regarding emission of greenhouse gases, there is a motivation to target the efficient chemical reduction of CO2. Re(I) integrated photosensitizers and catalysts, synthesized from commercially available ligands, are introduced with the selective CO2 reduction of formic acid, making for a unique class of Re(I) catalysts typically selective for CO as a reduction product. Furthermore, synthesized Zn(II) phosphino aminopyridine complexes are structurally and computationally characterized as well as observed to function as unprecedented electrocatalysts for the reduction of CO2 to formic acid and CO. Lastly, with the importance and popularity of N-heterocyclic carbenes (NHCs) as a class of ligands in the field of organometallic catalysis, six-membered perimidine based carbenes are further explored. Synthesis of a chelating pyridyl-perimidine NHC in addition to potential transition metal catalysts are also attempted.
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Hemming, Oliver. "Structure and reactivity of low-coordinate first-row transition metal complexes". Thesis, University of Manchester, 2018. https://www.research.manchester.ac.uk/portal/en/theses/structure-and-reactivity-of-lowcoordinate-firstrow-transition-metal-complexes(a7879b58-897e-4080-99f6-8551511a503a).html.

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Earth-abundant first-row transition metals have seen a renaissance in chemistry in recent years due to their relatively low toxicity and cost in comparison to precious metals. Furthermore open-shell transition metal complexes exhibit useful one-electron redox processes which contrasts to their heavier d block anologues. This thesis aims to synthesize and analyse the structure and reactivity of low-coordiante first-row transition metal complexes of from groups 7-9 with an aim to utilize these species in catalysis. The divalent compound [Co{N(SiMe3)2}2] reacts with the primary phosphines PhPH2 in the presence of an NHC ligand (IMe4) to yield the phosphinidene bridged dimer [(IMe4)2Co(µ-PMes)]2. The complex has interesting magnetic properties due to strong antiferromagnetic coupling between the two cobalt(II) centres. Increasing the steric bulk of the NHC yielded carbene-phosphinidene adducts (NHC·PAr). This transformation was shown to be catalytic. The structure and reactivity of complexes of the type [(NHC)xMn{(N(SiMe3)2}2] were investigated. The complexes exhibit similar structural properties to their iron and cobalt analogues; however their reactivity has been shown to differ. The addition of primary phosphines to complexes of the type [(NHC)xMn{N(SiMe3)2}2] yielded a range of manganese phosphide complexes. [Mn{N(SiMe3)2}2] also reacts with imidazolium salts at elevated temperatures to yield heteroleptic manganese NHC complexes. The reaction of [Mn{N(SiMe3)2}2] with IPr·HCl afforded the abnormal carbene complex [(aIPr)Mn{N(SiMe3)2}µ-Cl]2. A new monoanionic bidentate ligand is reported which has shown to be a useful ligand system to stabilize three-coordiante iron(II) complex. The reaction of [(L)Fe(Br)] with mesitylmagnesium Grignard or n-butyllithium yield the iron hydrocarbyls [(L)Fe(Mes)] and [(L)Fe(nBu)] with the latter being stable to β-hydrogen elimination. Finally [(L)Fe(nBu)] has been utilized as a pre-catalyst in the hydrophosphination of internal alkynes, showing selectivity for the E-isomeric vinylphosphine.
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Käß, Martina [Verfasser], i Karsten [Akademischer Betreuer] Meyer. "Late Transition Metal Complexes of Mixed NHC/Phenolate Tripodal Ligands for Small Molecule Activation / Martina Käß. Gutachter: Karsten Meyer". Erlangen : Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), 2014. http://d-nb.info/1075477379/34.

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Weiß, Daniel Traugott [Verfasser], Fritz E. [Akademischer Betreuer] Kühn i Richard W. [Akademischer Betreuer] Fischer. "Influence of Open Chain, Tetradentate NHC and NHC/Pyridine Hybrid Ligands on the Coordination and Electrochemistry of Late Transition Metal Complexes / Daniel Traugott Weiß. Betreuer: Fritz E. Kühn. Gutachter: Fritz E. Kühn ; Richard W. Fischer". München : Universitätsbibliothek der TU München, 2015. http://d-nb.info/1079974563/34.

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Schlagintweit, Jonas Felix [Verfasser], Fritz E. [Akademischer Betreuer] Kühn, Joao D. G. [Gutachter] Correia, Fritz E. [Gutachter] Kühn i Klaus [Gutachter] Köhler. "Transition Metal NHC Complexes in Oxidation Catalysis and Medicinal Chemistry / Jonas Felix Schlagintweit ; Gutachter: Joao D. G. Correia, Fritz E. Kühn, Klaus Köhler ; Betreuer: Fritz E. Kühn". München : Universitätsbibliothek der TU München, 2021. http://d-nb.info/1237815908/34.

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Simler, Thomas. "New transition metal complexes with functional N-heterocyclic carbene ligands for molecular activation". Thesis, Strasbourg, 2016. http://www.theses.fr/2016STRAF005.

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Le sujet de cette thèse porte sur l’étude de ligands hybrides incorporant un donneur carbène N-hétérocyclique (NHC). Les ligands phosphine-NHC construits sur le motif m-phénylène ont conduit à des complexes di- ou tétranucléaires d’Ag, Cu, Au et Ir, et à des complexes bimétalliques Ag/Cu et Ag/Ir par transmétallation sélective du site NHC. Dans le cas des ligands phosphino-picoline-NHC (PNC), la transmétallation des sels de Li ou K correspondants a permis d’isoler des complexes « pinceurs » dé-aromatisés du Cr, Fe et Co. La déprotonation du ligand bis(phosphinométhyl)pyridine (PNP) a été examinée, et les ligands dé-aromatisés mono- et bis-anioniques correspondants ont été utilisés dans des réactions de transmétallation vers le Cr(II) et Zr(IV). Différents modes de coordination des ligands dé-aromatisés, notamment une métallation de la position alpha-CHP, ont été observés. La substitution de la phosphine dans PNC par une fonction imine conduit à un ligand hybride « rédox non-innocent »
The purpose of this work is the synthesis and study of hybrid and potentially “pincer” ligands featuring an N-heterocyclic carbene (NHC) donor. The phosphine-NHC ligands based on the m-phenylene framework led to di- or tetranuclear Ag, Cu, Au and Ir complexes, and to bimetallic Ag/Cu and Ag/Ir complexes by selective transmetallation of the NHC. With the phosphino-picoline-NHC (PNC) ligands, transmetallation from the corresponding Li or K salts led to dearomatised Cr, Fe and Co “pincer” complexes. Deprotonation of the bis(phosphinomethyl)pyridine (PNP) ligand was also examined. The corresponding dearomatised mono- and bis-anionic ligands were isolated as Li or K salts and further used in transmetallation reactions towards Cr(II) and Zr(IV). Different coordination modes of the dearomatised ligands, including side-arm metallation, were observed. Substitution of the phosphine group in PNC by an imine donor led to a hybrid and “redox non-innocent” ligand
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Chang, I.-Hsin, i 張益信. "Heterotopic Bidentate NHC Ligands and Their Late Transition Metal Complexes-Synthesis and Catalysis". Thesis, 2010. http://ndltd.ncl.edu.tw/handle/79955598501757317683.

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博士
國立臺灣大學
化學研究所
98
In this thesis, the cationic rhodium (I) complexes bearing with hemilabile NHC bidentate ligands have been developed for the service as homogeneous catalysts using in the reactions such as hydrosilylation, hydroformylation, conjugate addition, and cycloaddition is studied. The cationic rhodium (I) complexes bearing NHC bidentate ligands in the form of [Rh(COD)LN-C]+X- or in the form of [Rh(COD)LS-C]+X- are successfully synthesized via transmetalation of silver NHC complex to cationic rhodium (I) metal source. The rhodium carbene carbon of the cationic rhodium (I) complexes (4a-4i) show 13C NMR resonance in 176.0-177.0 ppm and JRh-C = 53.0-54.0 Hz. The cationic rhodium (I) pyrimidyl NHC complexes display excellent catalytic activity for the hydrosilytion of acetophenones.(98% yield) The proton NMR of 4a shows the broad peaks in the COD and the singlet peak of the methylene protons of the thioether side arm at room temperature. To study the phenomenon in the solution containing 4a, the variable temperature NMR spectra are measured. According to the Gutowsky-Holm relationship24 and Eyring equation, the free energy of the sulfur inversion can be calculated in 48.61 KJmol-1. The rhodium (I) thioether NHC complexes can be effective catalysts for hydroformylation of aromatic or aliphatic olefins, but the selectivity of linear/branch aldehydes is fair (the ratio of linear/branch is almost 1). By adding phosphines, we can tune the ratio of linear/branch to be all branched aldehyde but the conversion is low (25% conversion). We can reduce the pressure of syn gas (H2/CO=1/1) to 300 psi instead of high pressure (1000 psi). The conversion of the hydroformylation can be quantitative and the ratio of the linear/branched aldehyde can be 0.93-1.23. The rhodium (I) thioether NHC complexes are efficient catalysts for the conjugate addition of boronic acids to enones. The catalyst loading was reduced to 0.5 mol% instead of the 3 mol% catalyst loading. The electron deficient or electron rich aryl boronic acids cannot retard the reaction. In spite of the bulky substituent such as o-methoxyphenyl boronic acid, the yield of Michael addition product was obtained in quantitative yield (98%). If thiol replaced the boronic acid, the thia- Michael addition can also be excellent yied (95%) by using rhodium thioether carbene catalyst. [2+2+2] Cycloaddition of DEAD or DMAD can be achieved in aqueous solution by using rhodium (I) thioether carbene catalyst. The DEAD and diyne can be different alkyne moiety and cyclotrimerize to form the cyclic benezene derivative. Pd (II) complexes bearing bidentate pyrimidyl-N-heterocyclic carbene ligands in the form of [LN-C]PdCl2 (LN-C = 2-pyrimidyl-imidazolylidene-NR, R = Me (5a), PhCH2 (5b), 2,6-Me2C6H3 (5d), 2,4,6-Me3C6H2 (5c)) have been synthesized and structurally characterized. The pyrimidyl-NHC ligand can facilitate these complexes for Suzuki-Miyaura cross coupling of aryl bromides and boronic acids.
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Holtz-Mulholland, Michael. "Synthesis of transition metal N-heterocyclic carbene complexes and applications in catalysis". Thèse, 2014. http://hdl.handle.net/1866/11407.

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Les ligands de carbènes N-hétérocycliques (NHC) qui possèdent une symétrie C1 attirent beaucoup l’attention dans la littérature. Le présent projet de recherche propose de synthétiser une nouvelle série de ligands NHC C1-symétriques avec deux groupements N-alkyles qui exploitent un relais chiral. Un protocole modulaire et efficace pour la synthèse des sels d’imidazolium chiraux qui servent comme préligands pour les NHC a été développé. Quelques-uns de ces nouveaux ligands ont été installés sur le cuivre et de l’or, créant de nouveaux complexes chiraux. Les nouveaux complexes à base de cuivre ont été évalués comme catalyseurs pour le couplage oxydatif de 2-naphthols. Les ligands C1-symmétriques ont fourni des meilleurs rendements que les ligands C2-symmétriques. Au cours de l’optimisation, des additifs ont été évalués; les additifs à base de pyridine ont fourni des énantiosélectivités modérées tandis que les additifs à base de malonate ont donné des meilleurs rendements de la réaction de couplage oxydatif. Ultérieurement, les additifs à base de malonate ont été appliqués envers l’hétérocouplage de 2-naphthols. Le partenaire de couplage qui est riche en électrons est normalement en grand excès à cause de sa tendance à dégrader. Avec le bénéfice de l’additif, les deux partenaires de couplage peuvent être utilisés dans des quantités équivalentes. La découverte de l’effet des additifs a permis le développement d’un protocole général pour l’hétérocouplage de 2-naphthols.
A new class of C1-symmetric N-heterocyclic carbene (NHC) ligands has been developed. The new ligands exploit a biaryl methyne as a chiral relay, and an N-methyl group as a reactivity controlling element. The precursors for the new ligands were synthesized via a modular scheme that allows for facile diversification. Several of the new ligands were installed onto both copper and gold, generating mono N-heterocyclic carbene transition metal complexes. The new C1-symmetric copper complexes were tested as catalysts for the synthesis of binaphthols via the oxidative coupling of electron poor 2-naphthols. The new C1-symmetric ligands afforded higher yields than their C2-symmetric counterparts. During the course of the optimization, small molecule additives were found to modulate the reactivity of the copper catalyst. Pyridine additives, such as 2-picoline, were found to induce low to moderate enantioselectivity in the oxidative coupling reaction, while diethylmalonate was found to improve the reaction yield without affecting the selectivity. The malonate additive was employed in the catalytic oxidative heterocoupling of electronically dissimilar 2-naphthols. The electron-rich coupling partner is normally added in a large excess due to its tendency to degrade. When the malonate additive is used, the coupling partners can be used in equimolar quantities. The discovery resulted in the development of a general protocol for the additive assisted aerobic oxidative heterocoupling of electronically dissimilar 2-naphthols.
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Części książek na temat "Transition Metal-NHC Complexes"

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Manna, Arunava, Abhineet Verma, Sumit K. Panja i Satyen Saha. "Recent Development of Carbenes: Synthesis, Structure, Photophysical Properties and Applications". W Carbene. IntechOpen, 2022. http://dx.doi.org/10.5772/intechopen.101413.

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Carbenes are highly reactive intermediates in organic synthesis. These divalent carbon species are generally transient in nature and cannot be isolated. However, they can form stabile metal complexes. Later on, the development of N-heterocyclic carbene (NHC) and other stable carbene led to the application of these carbon (II) donor ligands in the synthesis of complex natural products, transition metal catalysis, organo-catalysis and several other synthetic methodologies. Here in this short review, we will discuss the brief history of the development of carbenes, synthesis of stable carbenes (NHC in particular), and their applications in natural products synthesis transition metal chemistry/organometallics. In addition to synthesis and application, the chapter will consist of a detailed structural analysis of carbenes and exciting photophysics of this class of compounds. Special emphasis will be given to electronic structure. The role of carbene in the development of luminescent NHC transition metal complexes, the tuning of emission properties as well as their active role as photocatalysts in the reduction of CO2 will also be discussed.
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Ott, I. "Medicinal Chemistry of Metal N-Heterocyclic Carbene (NHC) Complexes". W Inorganic and Organometallic Transition Metal Complexes with Biological Molecules and Living Cells, 147–79. Elsevier, 2017. http://dx.doi.org/10.1016/b978-0-12-803814-7.00005-8.

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