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Recent Advance in Transition Metal Complexes and Their Applications II
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Recent Advance in Transition Metal Complexes and Their Applications II

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

Deadline for manuscript submissions: 31 October 2024 | Viewed by 2419

Special Issue Editor

Dr. Yungen Liu

E-Mail Website
Guest Editor
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China
Interests: C-H bond functionalization; non-precious transition metals; organic synthesis; catalysis; iron; nitrenoids; amination; oxidation
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Transition metal complexes are widely applied in various transformation reactions and are crucial in synthetic organic chemistry, especially for the preparation of complex natural molecules, pharmaceuticals and fine chemicals. Traditionally, these metal complexes heavily depend on the second- and third-row transition metals, such as palladium, rhodium and iridium. With the pressing need for green and sustainable synthetic processes, there has been a shift towards investigating catalytic reactions involving the use of first-row transition metal catalysts, which are more abundant and less toxic compared to their second- and third-row counterparts. This Special Issue presents the latest research on transition metal complexes and their applications, including characterization and property studies on structurally interesting metal complexes, applications of metal complexes in various transformation reactions and mechanistic studies. 

Dr. Yungen Liu
Guest Editor

Manuscript Submission Information

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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

  • transition metals
  • applications
  • organic synthesis
  • atom/group transfer
  • C-H bond activation/functionalization
  • pharmaceuticals and natural products

Related Special Issue

Published Papers (4 papers)

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Research

21 pages, 5417 KiB  
Article
Ruthenium p-Cymene Complexes Incorporating Substituted Pyridine–Quinoline-Based Ligands: Synthesis, Characterization, and Cytotoxic Properties
by Afroditi Kokkosi, Elpida Garofallidou, Nikolaos Zacharopoulos, Nikolaos Tsoureas, Konstantina Diamanti, Nikolaos S. Thomaidis, Antigoni Cheilari, Christina Machalia, Evangelia Emmanouilidou and Athanassios I. Philippopoulos
Molecules 2024, 29(13), 3215; https://doi.org/10.3390/molecules29133215 (registering DOI) - 6 Jul 2024
Abstract
Organometallic complexes of the formula [Ru(N^N)(p-cymene)Cl][X] (N^N = bidentate polypyridyl ligands, p-cymene = 1-methyl-4-(1-methylethyl)-benzene, X = counter anion), are currently studied as possible candidates for the potential treatment of cancer. Searching for new organometallic compounds with good to moderate cytotoxic [...] Read more.
Organometallic complexes of the formula [Ru(N^N)(p-cymene)Cl][X] (N^N = bidentate polypyridyl ligands, p-cymene = 1-methyl-4-(1-methylethyl)-benzene, X = counter anion), are currently studied as possible candidates for the potential treatment of cancer. Searching for new organometallic compounds with good to moderate cytotoxic activities, a series of mononuclear water-soluble ruthenium(II)–arene complexes incorporating substituted pyridine–quinoline ligands, with pending -CH2OH, -CO2H and -CO2Me groups in the 4-position of quinoline ring, were synthesized, for the first time, to study their possible effect to modulate the activity of the ruthenium p-cymene complexes. These include the [Ru(η6-p-cymene)(pqhyme)Cl][X] (X = Cl− (1-Cl), PF6− (1-PF6), pqhyme = 4-hydroxymethyl-2-(pyridin-2-yl)quinoline), [Ru(η6-p-cymene)(pqca)Cl][Cl] ((2-Cl), pqca = 4-carboxy-2-(pyridin-2-yl)quinoline), and [Ru(η6-p-cymene)(pqcame)Cl][X] (X = Cl− (3-Cl), PF6− (3-PF6), pqcame = 4-carboxymethyl-2-(pyridin-2-yl)quinoline) complexes, respectively. Identification of the complexes was based on multinuclear NMR and ATR-IR spectroscopic methods, elemental analysis, conductivity measurements, UV–Vis spectroscopic, and ESI-HRMS techniques. The solid-state structures of 1-PF6 and 3-PF6 have been elucidated by single-crystal X-ray diffraction revealing a three-legged piano stool geometry. This is the first time that the in vitro cytotoxic activities of these complexes are studied. These were conducted in HEK293T (human embryonic kidney cells) and HeLa cells (cervical cancer cells) via the MTT assay. The results show poor in vitro anticancer activities for the HeLa cancer cell lines and 3-Cl proved to be the most potent (IC50 > 80 μΜ). In both cell lines, the cytotoxicity of the ligand precursor pqhyme is significantly higher than that of cisplatin. Full article
(This article belongs to the Special Issue Recent Advance in Transition Metal Complexes and Their Applications II)
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17 pages, 8610 KiB  
Article
Infrared Photodissociation Spectroscopy of Dinuclear Vanadium-Group Metal Carbonyl Complexes: Diatomic Synergistic Activation of Carbon Monoxide
by ** Hu and Xuefeng Wang
Molecules 2024, 29(12), 2831; https://doi.org/10.3390/molecules29122831 - 14 Jun 2024
Viewed by 301
Abstract
The geometric structure and bonding features of dinuclear vanadium-group transition metal carbonyl cation complexes in the form of VM(CO)n+ (n = 9–11, M = V, Nb, and Ta) are studied by infrared photodissociation spectroscopy in conjunction with density functional calculations. [...] Read more.
The geometric structure and bonding features of dinuclear vanadium-group transition metal carbonyl cation complexes in the form of VM(CO)n+ (n = 9–11, M = V, Nb, and Ta) are studied by infrared photodissociation spectroscopy in conjunction with density functional calculations. The homodinuclear V2(CO)9+ is characterized as a quartet structure with CS symmetry, featuring two side-on bridging carbonyls and an end-on semi-bridging carbonyl. In contrast, for the heterodinuclear VNb(CO)9+ and VTa(CO)9+, a C2V sextet isomer with a linear bridging carbonyl is determined to coexist with the lower-lying CS structure analogous to V2(CO)9+. Bonding analyses manifest that the detected VM(CO)9+ complexes featuring an (OC)6M–V(CO)3 pattern can be regarded as the reaction products of two stable metal carbonyl fragments, and indicate the presence of the M–V d-d covalent interaction in the CS structure of VM(CO)9+. In addition, it is demonstrated that the significant activation of the bridging carbonyls in the VM(CO)9+ complexes is due in large part to the diatomic cooperation of M–V, where the strong oxophilicity of vanadium is crucial to facilitate its binding to the oxygen end of the carbonyl groups. The results offer important insight into the structure and bonding of dinuclear vanadium-containing transition metal carbonyl cluster cations and provide inspiration for the design of active vanadium-based diatomic catalysts. Full article
(This article belongs to the Special Issue Recent Advance in Transition Metal Complexes and Their Applications II)
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20 pages, 5701 KiB  
Article
Structural Design, Anticancer Evaluation, and Molecular Docking of Newly Synthesized Ni(II) Complexes with ONS-Donor Dithiocarbazate Ligands
by Claudia C. Gatto, Cássia de Q. O. Cavalcante, Francielle C. Lima, Érica C. M. Nascimento, João B. L. Martins, Brunna L. O. Santana, Ana C. M. Gualberto and Fabio Pittella-Silva
Molecules 2024, 29(12), 2759; https://doi.org/10.3390/molecules29122759 - 10 Jun 2024
Viewed by 527
Abstract
The current article reports the investigation of three new Ni(II) complexes with ONS-donor dithiocarbazate ligands: [Ni(L1)PPh3] (1), [Ni(L2)PPh3] (2), and [Ni(L2)Py] (3). Single-crystal X-ray analyses revealed [...] Read more.
The current article reports the investigation of three new Ni(II) complexes with ONS-donor dithiocarbazate ligands: [Ni(L1)PPh3] (1), [Ni(L2)PPh3] (2), and [Ni(L2)Py] (3). Single-crystal X-ray analyses revealed mononuclear complexes with a distorted square planar geometry and the metal centers coordinated with a doubly deprotonated dithiocarbazate ligand and coligand pyridine or triphenylphosphine. The non-covalent interactions were investigated by the Hirshfeld surface and the results revealed that the strongest interactions were π⋅⋅⋅π stacking interactions and non-classical hydrogen bonds C–H···H and C–H···N. Physicochemical and spectroscopic methods indicate the same structures in the solid state and solution. The toxicity effects of the free ligands and Ni(II) complexes were tested on the human breast cancer cell line MCF-7 and non-malignant breast epithelial cell line MCF-10A. The half-maximal inhibitory concentration (IC50) values, indicating that the compounds were potent in inhibiting cell growth, were obtained for both cell lines at three distinct time points. While inhibitory effects were evident in both malignant and non-malignant cells, all three complexes demonstrated lower IC50 values for malignant breast cell lines than their non-malignant counterparts, suggesting a stronger impact on cancerous cell lines. Furthermore, molecular docking studies were performed showing the complex (2) as a promising candidate for further therapeutic exploration. Full article
(This article belongs to the Special Issue Recent Advance in Transition Metal Complexes and Their Applications II)
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13 pages, 4979 KiB  
Article
Synthesis and Properties of Cobalt/Nickel-Iron-Antimony(III, V)-Oxo Tartrate Cluster-Based Compounds
by Weiyang Wen, Yanqi Wang, Tianyu Pan, Qianqian Hu, Hui** **ao, Nannan Wang, **aoqi Li, **nxiong Li, Bing Hu and **aoying Huang
Molecules 2024, 29(3), 591; https://doi.org/10.3390/molecules29030591 - 25 Jan 2024
Viewed by 947
Abstract
Two types of isostructural iron-cobalt/nickel-antimony-oxo tartrate cluster-based compounds, namely (H3O)(Me2NH2)[M(H2O)6]2[FeII2SbIII12(μ4-O)3(μ3-O)8(tta)6]·6H2 [...] Read more.
Two types of isostructural iron-cobalt/nickel-antimony-oxo tartrate cluster-based compounds, namely (H3O)(Me2NH2)[M(H2O)6]2[FeII2SbIII12(μ4-O)3(μ3-O)8(tta)6]·6H2O (M = Co (1); Ni (3)), H5/3[Co2.5FeII4/3FeIII3(H2O)13SbV1/3FeIII2/3(μ4-O)2(μ3-O)4SbIII6(μ3-O)2(tta)6]·2H2O (2) and H2[Ni2.25FeII1.5FeIII3(H2O)14SbV0.25FeIII0.75(μ4-O)2(μ3-O)4SbIII6(μ3-O)2(tta)6]·2H2O (4) (H4tta = tartaric acid) were synthesized via simple solvothermal reactions. All the clusters in the structures adopt sandwich configurations, that is, bilayer sandwich configuration in 1 and 3 and monolayer sandwich configuration in 2 and 4. Interestingly, the monolayer sandwiched compounds 2 and 4 represent rare examples of cluster-based compounds containing mixed-valence Sb(III, V), whose center of the intermediate layer is the co-occupied [FexSbV1−x]. This is different from that of previously reported sandwich-type antimony-oxo clusters in which the center position is either occupied by a transition metal ion or a Sb(V) alone. Thus, the discovery of title compounds 2 and 4 makes the evolution of center metal ion more complete, that is, from M, MxSbV1−x to SbV. All the title compounds were fully characterized, and the photocatalysis, proton conduction and magnetism of compounds 2 and 4 were studied. Full article
(This article belongs to the Special Issue Recent Advance in Transition Metal Complexes and Their Applications II)
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