Review
Chemistry, Physical
Sourav Sekhar Bera, Michal Szostak
Summary: This comprehensive review presents catalytic methods utilizing cobalt-NHC complexes, focusing on catalyst structure, the role of the NHC ligand, properties of the catalytic system, mechanism, and synthetic utility. The survey suggests that well-defined cobalt-NHC catalysts have great potential in the design and application of catalytic reactions using more abundant 3d transition metals.
Article
Chemistry, Multidisciplinary
Paul Zaby, Jan Blasius, Anna K. Mueller, Steven P. Nolan, Oldamur Holloczki
Summary: The formation mechanism of metal-N-heterocyclic carbene (NHC) complexes from imidazolium salts in the presence of weak bases was investigated through theoretical methods. Quantum chemical calculations revealed that both sodium acetate and trimethylamine facilitate complex formation. Molecular dynamics simulations showed that the ionic nature of the [AuCl2](-) and imidazolium ions, as well as the sodium acetate base, keep these species associated in the reaction mixture through ion pairing. The neutral amine, however, remains mostly separated from the other reaction partners, making it a significantly less effective base.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Inci Sogutlu, Mehdi Soltanzadeh, Handan Mert, Nihat Mert, Esmail Vessally
Summary: The study found that singlet carbenes are more stable than their corresponding triplets, and substituted ortho-thiophene carbenes in a W arrangement demonstrate the highest kinetic stability. Regardless of how organized, the stability order for fused rings is pyrrole > furan > thiophene > phosphole.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Inorganic & Nuclear
Waseem Mansour, Rami Suleiman, Wissam Iali, Mohammed Fettouhi, Bassam El Ali
Summary: A series of three 1,3-propanediyl bridged bis(N-heterocyclic carbene)palladium(II) complexes were studied for their catalytic activity and structure, with Pd-BNH3 showing the highest catalytic efficiency. The +I effect order of N-substituents of the ligand did not directly correlate with catalytic activity, but a direct correlation was found between the DFT calculated absolute softness of the complexes and their catalytic activity.
Article
Chemistry, Inorganic & Nuclear
Ceren Akpunar, Namik Ozdemir, Mert Olgun Karatas, Bulent Alici, Ismail Ozdemir
Summary: In this study, we synthesized five new coumarin-functionalised PEPPSI type Pd-NHC complexes to examine their catalyst properties. The complexes showed slightly distorted square-planar geometry and exhibited catalytic activity in the Suzuki-Miyaura reaction of phenylboronic acid and aryl bromide derivatives.
INORGANIC CHEMISTRY COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Rajendra S. Ghadwal
Summary: This review article aims to highlight recent advances in accessing stable iMICs, quantifying their properties, and exploring their applications in synthesis and catalysis. The synthetic viability and use of vicinal C4,C5-anionic dicarbenes (ADCs) based on a 1,3-imidazole framework are also presented. iMICs and ADCs have the potential to push the limit of classical NHCs by enabling access to conceptually new main-group heterocycles, radicals, molecular catalysts, ligand sets, and more.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Niklas F. Both, Anke Spannenberg, Haijun Jiao, Kathrin Junge, Matthias Beller
Summary: The use of bis(NHC) manganese(I) complexes 3 as catalysts for the hydrogenation of esters was investigated. Various aromatic and aliphatic esters were successfully hydrogenated at mild temperatures and low catalyst loadings using complexes 3 with KHBEt3 as additive, highlighting the efficiency of the novel catalytic system. Additionally, the versatility of the developed catalytic system was demonstrated by the hydrogenation of other substrate classes like ketones, nitriles, N-heteroarenes, and alkenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Inorganic & Nuclear
Yidan Wang, Bo Zhang, Shuai Guo
Summary: The combination of NHC and pincer framework in transition metal complexes has been widely studied and applied in various fields, including catalysis and optical material chemistry. This minireview focuses on the synthesis, reactivity study and applications of metal pincer NHCs.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Rizwan Ashraf, Zohra Khalid, Ayesha Sarfraz, Haq Nawaz Bhatti, Muhammad Adnan Iqbal, Mansoureh Nazari
Summary: Four new selenium-N-Heterocyclic Carbene adducts were synthesized from molten salts and analyzed through various techniques to confirm their structure and stability. These compounds showed promising anticancer potential with high activity in vitro cytotoxicity studies, low toxicity in interaction with proteins and hemolysis assay.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Inorganic & Nuclear
Thomas Scattolin, Andrea Piccin, Matteo Mauceri, Flavio Rizzolio, Nicola Demitri, Vincenzo Canzonieri, Fabiano Visentin
Summary: Newly synthesized palladium allyl complexes exhibit lower antiproliferative activity, with similar anticancer activity in two ovarian cancer cell lines, suggesting a different mechanism of action compared to platinum-based anticancer drugs. Some compounds show lower cytotoxicity on normal cells and higher selectivity towards cancer cells. Comparing the IC50 values of NHC/PTA complexes and their trifluoromethyl congeners indicates similar antiproliferative activity against cancer cells, but the absence of the CF3 group decreases selectivity towards them.
Article
Multidisciplinary Sciences
Alex Inayeh, Ryan R. K. Groome, Ishwar Singh, Alex J. Veinot, Felipe Crasto de Lima, Roberto H. Miwa, Cathleen M. Crudden, Alastair B. McLean
Summary: N-heterocyclic carbenes (NHCs) have emerged as a promising alternative to sulfur-based ligands for self-assembly on gold surfaces, but there are still many unanswered questions about their behavior on surfaces. This study examines fundamental questions such as NHC orientation, mobility, and self-assembly by analyzing NHC overlayers on Au(111).
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Jayaraman Selvakumar, Scott M. Simpson, Eva Zurek, Kuppuswamy Arumugam
Summary: This study successfully synthesized a series of iron bis(dithiolene) complexes with high yield and characterized them by NMR spectroscopy and X-ray diffraction. The research also showed that these iron complexes can release NHC upon electrochemical reduction, which can be used as a catalyst for synthesis.
INORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Ziyan Zhang, Nikita Kvasovs, Anastasiia Dubrovina, Vladimir Gevorgyan
Summary: This method utilizes visible light-induced and Bronsted acid-assisted generation of hybrid palladium C(sp(3))-centered radical intermediate, enabling efficient transformation of a wide range of vinyl arenes, heteroarenes, and diazo compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Federica Tufano, Federica Santulli, Fabia Grisi, Marina Lamberti
Summary: Two zinc complexes with NHC ligands were synthesized and studied for their behavior in the Ring-Opening Polymerization of lactides, showing efficiency as initiators with molecular weights dependent on cocatalysts. Microstructural analysis revealed enriched heterotactic PLA, with kinetic parameters compared between different conditions and reactions showing pseudo-first-order dependence on monomer concentration. Reactivity studies aimed to uncover the active species in polymerization processes with different catalytic systems, including zinc complexes alone or in combination with neutral or ionic cocatalysts.
Article
Chemistry, Inorganic & Nuclear
Sebastien G. Guillet, Ishfaq Ibni Hashim, Marek Belis, Kristof Van Hecke, Catherine S. J. Cazin, Steven. P. Nolan
Summary: A simple synthetic method for synthesizing various [Rh(acac)(CO)(NHC)] complexes is presented. In situ infrared monitoring provides valuable information on the reaction mechanism, including the identification of a crucial intermediate. Understanding the reaction mechanism has led to the discovery of novel pathways to commonly used congeners.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
