Review
Chemistry, Applied
Eve M. Poland, Curtis C. Ho
Summary: This Minireview presents recent developments in photoactive/photoluminescent N-heterocyclic carbene (NHC) transition metal complexes and discusses their viability as catalysts in bond-forming photocatalysis. Key structural motifs and photophysical properties of these complexes are summarized. Representative examples of their applications as catalysts in bond-forming photochemical reactions are showcased, highlighting the state-of-the-art and future opportunities for this exciting class of NHC transition metal complexes.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Biochemical Research Methods
Fady Nahra, Nikolaos Tzouras, Alba Collado, Steven P. Nolan
Summary: N-heterocyclic carbene gold(I) chloride and hydroxide complexes are commonly used as synthetic reagents and efficient catalysts. This study describes a straightforward and practical method for synthesizing mononuclear gold complexes with high yields, as well as the synthesis of a mononuclear gold(I) hydroxide complex and an improved synthesis method for a dinuclear gold(I) hydroxide complex. This methodology offers advantages such as the use of sustainable reaction solvents and commercially available starting materials.
Article
Chemistry, Inorganic & Nuclear
Clemens Kaussler, Darren Wragg, Claudia Schmidt, Guillermo Moreno-Alcantar, Christian Jandl, Johannes Stephan, Roland A. Fischer, Stefano Leoni, Angela Casini, Riccardo Bonsignore
Summary: This study focuses on improving the design of metal complexes as stabilizers of noncanonical DNA secondary structures. A series of cyclic dinuclear Au(I) N-heterocyclic carbene complexes based on xanthine and benzimidazole ligands have been synthesized and characterized. The compounds show stabilization properties towards G-quadruplexes (G4s) and moderate antiproliferative activity in human cancer cells. The binding modes and free energy landscape of the most active compound have been studied using metadynamics.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Junbeom Park, Jaelim Kim, Gu Yoon Jeong, Youngsuk Kim, Eunsung Lee
Summary: This study investigates the electron and proton transfer chemistry of N-heterocyclic carbene nitric oxide radical compounds and prepares a variety of nitrosyl derivatives. The reactions of these derivatives resemble those of transition metal nitrosyl complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Physical
Paulina Baczewska, Katarzyna Sniady, Wioletta Kosnik, Michal Michalak
Summary: N-Heterocyclic carbene (NHC) ligands have become a privileged structural motif in modern homogeneous and heterogeneous catalysis, especially in the area of carbon-carbon bond formation. NHC ligands derived from acenaphthylene with a pi-extended system show superior sigma-donor capabilities, enhancing catalytic activity and stability in transition metal complexes.
Review
Polymer Science
Isha Jain, Payal Malik
Summary: Metal-N-heterocyclic carbene complexes (M-NHCs) have shown great potential as a catalytic system for the synthesis of various biodegradable polymers via ring opening polymerization. This review provides an overview of the field's major achievements and developments from 2004 to 2020, with a focus on the structure-activity relationship of M-NHC complexes.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Chemistry, Applied
Vanessa Vethacke, Vanessa Claus, Martin C. Dietl, Daniel Ehjeij, Arne Meister, Jonas F. Huber, Leon K. Paschai Darian, Matthias Rudolph, Frank Rominger, A. Stephen K. Hashmi
Summary: A variety of unsymmetric diaryl gold N-acyclic carbene (NAC) complexes were successfully synthesized by three different methods, allowing access to new complexes and overcoming previous limitations in the isonitrile route. These new complexes also proved to be successful as pre-catalysts in gold-catalyzed phenol synthesis.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Matthew P. Sullivan, Monika Cziferszky, Iogann Tolbatov, Dianna Truong, Davide Mercadante, Nazzareno Re, Ronald Gust, David C. Goldstone, Christian G. Hartinger
Summary: Metal complexes exhibit different binding behaviors with proteins, with Ru and Rh complexes targeting surface l-histidine residues, while Os and Ir derivatives predominantly located in electronegative binding pockets after ligand exchange. Computational studies support the binding profiles and suggest the role of protein microenvironment in eliciting selectivity for specific binding sites on the protein.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Hui Shen, Lingzheng Wang, Omar Lopez-Estrada, Chengyi Hu, Qingyuan Wu, Dongxu Cao, Sami Malola, Boon K. Teo, Hannu Hakkinen, Nanfeng Zheng
Summary: Copper-hydride nanoclusters stabilized by bidentate N-heterocyclic carbenes and thiolates were successfully synthesized and characterized, showing an unprecedented ultra-high thermal stability. The unique superstructure and controlled properties of the copper nanoclusters demonstrate the power of NHCs in the design of polyhydrido copper clusters.
Article
Chemistry, Organic
Killari Satyam, Jakkula Ramarao, Surisetti Suresh
Summary: The NHC-catalyzed intramolecular benzoin condensation-oxidation allows for the expedient synthesis of diverse cyclic 1,2-diketones incorporated in dibenzo-fused seven-membered heterocycles in good to excellent yields under ambient conditions. The transformation appears to proceed through the benzoin intermediate followed by aerobic oxidation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Simon Stenkvist, Sara Bacaicoa, Ellymay Goossens, Henrik Sunden
Summary: The use of oxidative N-heterocyclic carbene (NHC) catalysis has gained significant interest due to the ease of transforming simple starting materials into highly functionalized products. However, the use of stoichiometric amounts of high molecular weight oxidants usually generates equivalent amounts of waste. To address this issue, the use of oxygen as the terminal oxidant in NHC catalysis has been developed. This review covers the development of aerobic oxidative carbene catalysis, including NHC-catalyzed reactions with oxygen, strategies for oxygen activation, and selectivity issues under aerobic conditions.
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, Multidisciplinary
Ichraf Slimani, Serap Sahin-Bolukbasi, Mustafa Ulu, Enes Evren, Nevin Gurbuz, Ilknur Ozdemir, Naceur Hamdi, Ismail Ozdemir
Summary: A series of rhodium(i) complexes with N-heterocyclic carbene ligands showed high in vitro cytotoxic activity against human cancer cells, with complex 2b exhibiting the most selective cytotoxic activity. These complexes demonstrated greater cytotoxicity against cancer cells compared to established anticancer agents cisplatin and 5-fluorouracil.
NEW JOURNAL OF CHEMISTRY
(2021)
Review
Chemistry, Inorganic & Nuclear
Sai Zhao, Zhibing Yang, Guizhi Jiang, Sheng Huang, Mianli Bian, Yunlong Lu, Wukun Liu
Summary: NHCs have been introduced as a new platform for the development of anticancer metal complexes, with platinum NHC complexes showing comparable activities to cisplatin and exhibiting different mechanisms of action, including the induction of biochemical hallmarks of immunogenic cell death (ICD) as a type II ICD inducer. These features make them promising candidates in the field of anticancer research.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Alexander S. Mikherdov, Mingoo Jin, Hajime Ito
Summary: In this study, it was demonstrated experimentally that Au(i) metal center can form predictable halogen bonding interactions with neutral Au(i) complexes. The nature of these interactions was elucidated through various experimental and computational techniques, revealing a connection between the structure and properties of the metal center as XB acceptors.