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Organometallic Complexes: Fundamentals and Applications
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Organometallic Complexes: Fundamentals and Applications

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (30 June 2022) | Viewed by 10471

Special Issue Editors

Dr. Sandra Bolaño

E-Mail Website
Guest Editor
Departamento de Química Inorgánica, Universidade de Vigo, Campus Universitario, 36310 Vigo, Spain
Interests: organometallics; metallaaromatics; C-H activation; C-heteroatom coupling; applications in material science
Dr. Maria Talavera

E-Mail Website
Guest Editor
Department of Chemistry, Humboldt–Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany
Interests: organometallics; metallaaromatics; fluorine chemistry; C-F bond activation; catalysis

Special Issue Information

Dear Colleagues,

Organometallic chemistry has hugely advanced during the last decades. The importance of disclosing the fundamentals behind every process and property to reach certain applications has increased over the years. Nowadays, it is not only important to achieve a reaction, but also understand such reactions. The role of organometallic chemistry in this field is key for developing new materials and processes in order to improve our living conditions. Therefore, in this Special Issue, we aim to present interesting research not only regarding applications, but also fundamental research related to organometallic chemistry. 

Dr. Sandra Bolaño
Dr. Maria Talavera
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • organometallics
  • transition metals
  • fundamental chemistry
  • synthesis
  • catalysis

Published Papers (6 papers)

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Research

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21 pages, 3618 KiB  
Article
Synthesis, Characterization, and Cytotoxicity Studies of N-(4-Methoxybenzyl) Thiosemicarbazone Derivatives and Their Ruthenium(II)-p-cymene Complexes
by Mónica Martínez-Estévez, Soledad García-Fontán, Saray Argibay-Otero, Inmaculada Prieto and Ezequiel M. Vázquez-López
Molecules 2022, 27(22), 7976; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27227976 - 17 Nov 2022
Cited by 3 | Viewed by 1266
Abstract
The reaction of [Ru2Cl2(μ-Cl)2(η6-p-cymene)2] with two thiosemicarbazones obtained by the condensation of N-(4-methoxybenzyl) thiosemicarbazide and 1,4-hydroxy-3-methoxyphenyl)ethan-1-one (HL1) or 2-fluoro-4-hydroxybenzaldehyde (HL2) was studied. The cationic complexes [...] Read more.
The reaction of [Ru2Cl2(μ-Cl)2(η6-p-cymene)2] with two thiosemicarbazones obtained by the condensation of N-(4-methoxybenzyl) thiosemicarbazide and 1,4-hydroxy-3-methoxyphenyl)ethan-1-one (HL1) or 2-fluoro-4-hydroxybenzaldehyde (HL2) was studied. The cationic complexes of formula [RuCl(η6-p-cymene)(HL)]+ were isolated as solid chloride and trifluoromethylsulfate (TfO) salts. A study of the solid state and NMR spectra suggests the presence in the material of two isomers that differ in the configuration in the iminic bond, C2=N3, of the coordinated thiosemicarbazone in the triflate salts and only the E isomer in the chloride. An X-ray study of single crystals of the complexes supports this hypothesis. The thiosemicarbazone ligand coordinates with the ruthenium center through the iminic and sulfur atoms to form a five-membered chelate ring. Furthermore, the isolation of single crystals containing the thiosemicarbazonate complex [Ru2(μ-L2)2(η6-p-cymene)2]2+ suggests the easy labilization of the coordinated chloride in the complex. The redox behavior of the ligands and complexes was evaluated by cyclic voltammetry. It seems to be more difficult to oxidize the complex derived from HL1 than HL2. The ability of the complexes to inhibit cell growth against the NCI-H460, A549 and MDA-MB-231 lines was evaluated. The complexes did not show greater potency than cisplatin, although they did have greater efficacy, especially for the complex derived from HL1. Full article
(This article belongs to the Special Issue Organometallic Complexes: Fundamentals and Applications)
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12 pages, 1320 KiB  
Article
Cyclometallated Palladium(II) Complexes: An Approach to the First Dinuclear Bis(iminophosphorane)phosphane-[C,N,S] Metallacycle
by Marcos Rúa-Sueiro, Paula Munín-Cruz, Adolfo Fernández, Juan M. Ortigueira, María Teresa Pereira and José M. Vila
Molecules 2022, 27(20), 7043; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27207043 - 19 Oct 2022
Viewed by 1220
Abstract
Treatment of bis(iminophosphorane)phosphane ligands 2a–2e with Li2PdCl4 gave a set of novel diphosphane-derived complexes bearing two metallacycle rings, each one enclosing a P=N double bond: the unprecedented bis(iminophosphorane)phosphane-[C,N,S] palladacycles. In the case of the ligand derived from bis(diphenylphosphino)methane, [...] Read more.
Treatment of bis(iminophosphorane)phosphane ligands 2a–2e with Li2PdCl4 gave a set of novel diphosphane-derived complexes bearing two metallacycle rings, each one enclosing a P=N double bond: the unprecedented bis(iminophosphorane)phosphane-[C,N,S] palladacycles. In the case of the ligand derived from bis(diphenylphosphino)methane, 2a, both the single and the double palladacycle complexes were obtained. Reaction of 3a with bis(diphenylphosphino)ethane did not yield the expected product with the diphosphane bonded to both palladium atoms, but rather the novel coordination compound 5. The crystal structures of 3c and 5 are described. Full article
(This article belongs to the Special Issue Organometallic Complexes: Fundamentals and Applications)
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15 pages, 1968 KiB  
Article
Preparation of Mixed Bis-N-Heterocyclic Carbene Rhodium(I) Complexes
by Ramón Azpíroz, Mert Olgun Karataş, Vincenzo Passarelli, Ismail Özdemir, Jesús J. Pérez-Torrente and Ricardo Castarlenas
Molecules 2022, 27(20), 7002; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27207002 - 18 Oct 2022
Viewed by 1185
Abstract
A series of mixed bis-NHC rhodium(I) complexes of type RhCl(η2-olefin)(NHC)(NHC’) have been synthesized by a stepwise reaction of [Rh(μ-Cl)(η2-olefin)2]2 with two different NHCs (NHC = N-heterocyclic carbene), in which the steric hindrance of both [...] Read more.
A series of mixed bis-NHC rhodium(I) complexes of type RhCl(η2-olefin)(NHC)(NHC’) have been synthesized by a stepwise reaction of [Rh(μ-Cl)(η2-olefin)2]2 with two different NHCs (NHC = N-heterocyclic carbene), in which the steric hindrance of both NHC ligands and the η2-olefin is critical. Similarly, new mixed coumarin-functionalized bis-NHC rhodium complexes have been prepared by a reaction of mono NHC complexes of type RhCl(NHC-coumarin)(η2,η2-cod) with the corresponding azolium salt in the presence of an external base. Both synthetic procedures proceed selectively and allow the preparation of mixed bis-NHC rhodium complexes in good yields. Full article
(This article belongs to the Special Issue Organometallic Complexes: Fundamentals and Applications)
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11 pages, 1893 KiB  
Article
Heteroctanuclear Au4Ag4 Cluster Complexes of 4,5-Diethynylacridin-9-One with Luminescent Mechanochromism
by Pei Xie, Jin-Yun Wang, Ya-Zi Huang, Xue-Meng Wu and Zhong-Ning Chen
Molecules 2022, 27(7), 2127; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27072127 - 25 Mar 2022
Cited by 2 | Viewed by 1703
Abstract
Two heteroctanuclear Au4Ag4 cluster complexes of 4,5-diethynylacridin-9-one (H2L) were prepared through the self-assembly reactions of [Au(tht)2](CF3SO3), Ag(tht)(CF3SO3), H2L and PPh3 or PPh2Py (2-(diphenylphosphino)pyridine). [...] Read more.
Two heteroctanuclear Au4Ag4 cluster complexes of 4,5-diethynylacridin-9-one (H2L) were prepared through the self-assembly reactions of [Au(tht)2](CF3SO3), Ag(tht)(CF3SO3), H2L and PPh3 or PPh2Py (2-(diphenylphosphino)pyridine). The Au4Ag4 cluster consists of a [Au4L4]4− and four [Ag(PPh3)]+ or [Ag(PPh2Py)]+ units with Au4L4 framework exhibiting a twisted paper clip structure. In CH2Cl2 solutions at ambient temperature, both compounds show ligand fluorescence at ca. 463 nm as well as phosphorescence at 650 nm for 1 and 630 nm for 2 resulting from admixture of 3IL (intraligand) of L ligand, 3LMCT (from L ligand to Au4Ag4) and 3MC (metal-cluster) triplet states. Crystals or crystalline powders manifest bright yellow-green phosphorescence with vibronic-structured emission bands at 530 (568sh) nm for complex 1 and 536 (576sh) nm for complex 2. Upon mechanical grinding, yellow-green emission in the crystalline state is dramatically converted to red luminescence centered at ca. 610 nm with a drastic redshift of the emission after crystal packing is destroyed. Full article
(This article belongs to the Special Issue Organometallic Complexes: Fundamentals and Applications)
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14 pages, 3320 KiB  
Article
Ruthenafuran Complexes Supported by the Bipyridine-Bis(diphenylphosphino)methane Ligand Set: Synthesis and Cytotoxicity Studies
by Chi-Fung Yeung, Sik-Him Tang, Zhe Yang, Tsun-Yin Li, Ka-Kit Li, Yuen-Man Chan, Hau-Lam Shek, Kai-Wa Io, King-Ting Tam, Shek-Man Yiu, Man-Kit Tse and Chun-Yuen Wong
Molecules 2022, 27(5), 1709; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27051709 - 05 Mar 2022
Cited by 3 | Viewed by 1979
Abstract
Mononuclear and dinuclear Ru(II) complexes cis-[Ru(κ2-dppm)(bpy)Cl2] (1), cis-[Ru(κ2-dppe)(bpy)Cl2] (2) and [Ru2(bpy)2(μ-dpam)2(μ-Cl)2](Cl)2 ([3](Cl)2) were prepared from the [...] Read more.
Mononuclear and dinuclear Ru(II) complexes cis-[Ru(κ2-dppm)(bpy)Cl2] (1), cis-[Ru(κ2-dppe)(bpy)Cl2] (2) and [Ru2(bpy)2(μ-dpam)2(μ-Cl)2](Cl)2 ([3](Cl)2) were prepared from the reactions between cis(Cl), cis(S)-[Ru(bpy)(dmso-S)2Cl2] and diphosphine/diarsine ligands (bpy = 2,2′-bipyridine; dppm = 1,1-bis(diphenylphosphino)methane; dppe = 1,2-bis(diphenylphosphino)ethane; dpam = 1,1-bis(diphenylarsino)methane). While methoxy-substituted ruthenafuran [Ru(bpy)(κ2-dppe)(C^O)]+ ([7]+; C^O = anionic bidentate [C(OMe)CHC(Ph)O]− chelate) was obtained as the only product in the reaction between 2 and phenyl ynone HC≡C(C=O)Ph in MeOH, replacing 2 with 1 led to the formation of both methoxy-substituted ruthenafuran [Ru(bpy)(κ2-dppm)(C^O)]+ ([4]+) and phosphonium-ring-fused bicyclic ruthenafuran [Ru(bpy)(P^C^O)Cl]+ ([5]+; P^C^O = neutral tridentate [(Ph)2PCH2P(Ph)2CCHC(Ph)O] chelate). All of these aforementioned metallafuran complexes were derived from Ru(II)–vinylidene intermediates. The potential applications of these metallafuran complexes as anticancer agents were evaluated by in vitro cytotoxicity studies against cervical carcinoma (HeLa) cancer cell line. All the ruthenafuran complexes were found to be one order of magnitude more cytotoxic than cisplatin, which is one of the metal-based anticancer agents being widely used currently. Full article
(This article belongs to the Special Issue Organometallic Complexes: Fundamentals and Applications)
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Review

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31 pages, 8073 KiB  
Review
Guanidinates as Alternative Ligands for Organometallic Complexes
by Fernando Carrillo-Hermosilla, Rafael Fernández-Galán, Alberto Ramos and David Elorriaga
Molecules 2022, 27(18), 5962; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27185962 - 13 Sep 2022
Cited by 7 | Viewed by 2509
Abstract
For decades, ligands such as phosphanes or cyclopentadienyl ring derivatives have dominated Coordination and Organometallic Chemistry. At the same time, alternative compounds have emerged that could compete either for a more practical and accessible synthesis or for greater control of steric and electronic [...] Read more.
For decades, ligands such as phosphanes or cyclopentadienyl ring derivatives have dominated Coordination and Organometallic Chemistry. At the same time, alternative compounds have emerged that could compete either for a more practical and accessible synthesis or for greater control of steric and electronic properties. Guanidines, nitrogen-rich compounds, appear as one such potential alternatives as ligands or proligands. In addition to occurring in a plethora of natural compounds, and thus in compounds of pharmacological use, guanidines allow a wide variety of coordination modes to different metal centers along the periodic table, with their monoanionic chelate derivatives being the most common. In this review, we focused on the organometallic chemistry of guanidinato compounds, discussing selected examples of coordination modes, reactivity and uses in catalysis or materials science. We believe that these amazing ligands offer a new promise in Organometallic Chemistry. Full article
(This article belongs to the Special Issue Organometallic Complexes: Fundamentals and Applications)
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