Metal Arene Complexes

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (31 March 2022) | Viewed by 17037

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Institut de Chimie, Université de Neuchâtel, Avenue de Bellevaux 51, CH-2000 Neuchâtel, Switzerland
Interests: metalla-assemblies; supramolecular chemistry; host-guest chemistry; metal-based drugs; organometallic chemistry; X-ray crystallography
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Dear Colleagues,

For very good reasons, metal arene complexes are among the most studied organometallic complexes. In such complexes, the arene ligand plays crucial roles that are often underestimated. In catalysis, for example, the arene ligand is not considered directly involved in the catalytic process; however, it ensures electronic and structural stability at the metal center, and if properly designed, it can introduce steric hindrance and dictate how the substrate will bind to the metal. In medicinal chemistry, the arene is also important, despite being often seen as an innocent ligand. In biological media, it can modulate the solubility of the complex, and accordingly trigger different responses in cells. In supramolecular chemistry, the presence of the arene limits the number of coordination sites available on the metal, thus, allowing geometric control during the assembly process. These are only a few examples, where the characteristics of metal arene complexes have been nicely exploited. In this Special Issue, we would like to gather all kinds of studies in which the metal arene complex is central. Therefore, all contributions involving metal arene complexes are welcome.

Prof. Dr. Bruno Therrien
Guest Editor

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Keywords

  • Arene ligand
  • Catalysis
  • Bioinorganic chemistry
  • Supramolecular chemistry
  • Coordination complexes
  • Organometallic chemistry
  • Metal-based drugs
  • Piano-stool complexes

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Published Papers (4 papers)

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Research

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25 pages, 17465 KiB  
Article
Synthesis and Antiparasitic Activity of New Conjugates—Organic Drugs Tethered to Trithiolato-Bridged Dinuclear Ruthenium(II)–Arene Complexes
by Oksana Desiatkina, Serena K. Johns, Nicoleta Anghel, Ghalia Boubaker, Andrew Hemphill, Julien Furrer and Emilia Păunescu
Inorganics 2021, 9(8), 59; https://doi.org/10.3390/inorganics9080059 - 21 Jul 2021
Cited by 7 | Viewed by 3467
Abstract
Tethering known drugs to a metalorganic moiety is an efficient approach for modulating the anticancer, antibacterial, and antiparasitic activity of organometallic complexes. This study focused on the synthesis and evaluation of new dinuclear ruthenium(II)–arene compounds linked to several antimicrobial compounds such as dapsone, [...] Read more.
Tethering known drugs to a metalorganic moiety is an efficient approach for modulating the anticancer, antibacterial, and antiparasitic activity of organometallic complexes. This study focused on the synthesis and evaluation of new dinuclear ruthenium(II)–arene compounds linked to several antimicrobial compounds such as dapsone, sulfamethoxazole, sulfadiazine, sulfadoxine, triclosan, metronidazole, ciprofloxacin, as well as menadione (a 1,4-naphtoquinone derivative). In a primary screen, 30 compounds (17 hybrid molecules, diruthenium intermediates, and antimicrobials) were assessed for in vitro activity against transgenic T. gondii tachyzoites constitutively expressing β-galactosidase (T. gondii β-gal) at 0.1 and 1 µM. In parallel, the cytotoxicity in noninfected host cells (human foreskin fibroblasts, HFF) was determined by an alamarBlue assay. When assessed at 1 µM, five compounds strongly impaired parasite proliferation by >90%, and HFF viability was retained at 50% or more, and they were further subjected to T. gondii β-gal dose-response studies. Two compounds, notably 11 and 13, amide and ester conjugates with sulfadoxine and metronidazole, exhibited low IC50 (half-maximal inhibitory concentration) values 0.063 and 0.152 µM, and low or intermediate impairment of HFF viability at 2.5 µM (83 and 64%). The nature of the anchored drug as well as that of the linking unit impacted the biological activity. Full article
(This article belongs to the Special Issue Metal Arene Complexes)
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12 pages, 2656 KiB  
Article
Synthesis and Structural Characterization of Half-Sandwich Arene–Ruthenium(II) Complexes with Bis(imidazol-1-yl)methane, Imidazole and Benzimidazole
by Vladislava V. Matveevskaya, Dmitry I. Pavlov, Denis G. Samsonenko, Ekaterina A. Ermakova, Lyubov S. Klyushova, Sergey V. Baykov, Vadim P. Boyarskiy and Andrei S. Potapov
Inorganics 2021, 9(5), 34; https://doi.org/10.3390/inorganics9050034 - 4 May 2021
Cited by 6 | Viewed by 2909
Abstract
Mono- and binuclear arene–ruthenium(II) complexes with imidazole-containing ligands were prepared by the reaction of the ligands (L1 = bis(imidazole-1-yl)methane; ImH = 1H-Imidazole; BImH = 1H-Benzimidazole) with [(p-cym)Ru(µ-Cl)2]2 dimers. When bis(imidazole-1-yl)methane reacted with [( [...] Read more.
Mono- and binuclear arene–ruthenium(II) complexes with imidazole-containing ligands were prepared by the reaction of the ligands (L1 = bis(imidazole-1-yl)methane; ImH = 1H-Imidazole; BImH = 1H-Benzimidazole) with [(p-cym)Ru(µ-Cl)2]2 dimers. When bis(imidazole-1-yl)methane reacted with [(p-cym)Ru(µ-Cl)2]2 in methanol, a binuclear complex of the type [Ru2(L1)2(p-cym)2Cl2]Cl2 (2) with cyclic structure was synthesized, whereas by using acetonitrile as a solvent under the same reaction conditions, an unexpected C–N bond cleavage was observed, and a complex of formula [Ru(ImH)2(p-cym)Cl]Cl (1) with coordinated imidazole molecules was obtained. Another type of arene–ruthenium complex [Ru(BImH)(p-cym)Cl2] (3) was obtained by the reaction of benzimidazole and [(p-cym)Ru(µ-Cl)2]2. All compounds were characterized by spectral (FT-IR, NMR 1H, 13C) and single-crystal X-ray diffraction methods; their catalytic activity in transfer hydrogenation and the cytotoxicity against MCF-7 and HepG2 cells were evaluated. Full article
(This article belongs to the Special Issue Metal Arene Complexes)
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Review

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30 pages, 106445 KiB  
Review
Arene-Osmium(II) Complexes in Homogeneous Catalysis
by Pascale Crochet and Victorio Cadierno
Inorganics 2021, 9(7), 55; https://doi.org/10.3390/inorganics9070055 - 12 Jul 2021
Cited by 4 | Viewed by 3762
Abstract
Although the application of arene-osmium(II) complexes in homogeneous catalysis has been much less studied than that of their ruthenium analogues, different works have shown that, in some instances, a comparable or even superior effectiveness can be achieved with this particular class of compounds. [...] Read more.
Although the application of arene-osmium(II) complexes in homogeneous catalysis has been much less studied than that of their ruthenium analogues, different works have shown that, in some instances, a comparable or even superior effectiveness can be achieved with this particular class of compounds. This review article focuses on the catalytic applications of arene-osmium(II) complexes. Among others, transfer hydrogenation, hydrogenation, oxidation, and nitrile hydration reactions, as well as different C-C bond forming processes, are comprehensively discussed. Full article
(This article belongs to the Special Issue Metal Arene Complexes)
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24 pages, 1400 KiB  
Review
Anticancer Half-Sandwich Rhodium(III) Complexes
by Klaudia Máliková, Lukáš Masaryk and Pavel Štarha
Inorganics 2021, 9(4), 26; https://doi.org/10.3390/inorganics9040026 - 8 Apr 2021
Cited by 30 | Viewed by 5336
Abstract
Platinum-based anticancer drugs are most likely the most successful group of bioinorganic compounds. Their apparent disadvantages have led to the development of anticancer compounds of other noble metals, resulting in several ruthenium-based drugs which have entered clinical trials on oncological patients. Besides ruthenium, [...] Read more.
Platinum-based anticancer drugs are most likely the most successful group of bioinorganic compounds. Their apparent disadvantages have led to the development of anticancer compounds of other noble metals, resulting in several ruthenium-based drugs which have entered clinical trials on oncological patients. Besides ruthenium, numerous rhodium complexes have been recently reported as highly potent antiproliferative agents against various human cancer cells, making them potential alternatives to Pt- and Ru-based metallodrugs. In this review, half-sandwich Rh(III) complexes are overviewed. Many representatives show higher in vitro potency than and different mechanisms of action (MoA) from the conventional anticancer metallodrugs (cisplatin in most cases) or clinically studied Ru drug candidates. Furthermore, some of the reviewed Rh(III) arenyl complexes are also anticancer in vivo. Pioneer anticancer organorhodium compounds as well as the recent advances in the field are discussed properly, and adequate attention is paid to their anticancer activity, solution behaviour and various processes connected with their MoA. In summary, this work summarizes the types of compounds and the most important biological results obtained in the field of anticancer half-sandwich Rh complexes. Full article
(This article belongs to the Special Issue Metal Arene Complexes)
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