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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: closed (31 October 2024) | Viewed by 11233

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

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Keywords

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

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Related Special Issue

Published Papers (6 papers)

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Research

19 pages, 5662 KiB  
Article
Synthesis, Characterization and Catalytic/Antimicrobial Activities of Some Transition Metal Complexes Derived from 2-Floro-N-((2-Hydroxyphenyl)Methylene)Benzohydrazide
by Ahmed K. Hijazi, Ziyad A. Taha, Dua’a K. Issa, Heba M. Alshare, Waleed M. Al-Momani, Ali Elrashidi and Ahmad S. Barham
Molecules 2024, 29(23), 5758; https://doi.org/10.3390/molecules29235758 - 5 Dec 2024
Cited by 1 | Viewed by 1162
Abstract
Background: In the last few decades, the field of coordination chemistry has grown very fast, especially in the fields of pharmaceutical, biological and catalytic studies. In ancient times, metals were thought to be beneficial to health issues but nowadays the link between organic–metal [...] Read more.
Background: In the last few decades, the field of coordination chemistry has grown very fast, especially in the fields of pharmaceutical, biological and catalytic studies. In ancient times, metals were thought to be beneficial to health issues but nowadays the link between organic–metal substances and different industrial and medicinal properties is well established. Methods: A Schiff base ligand (2-fluoro-N’-[(E)-2-hydroxyphenyl) methylene] benzohydrazide) was reacted with a series of transition metals to produce complexes with a general formula [ML2(NO3)]NO3.nH2O, where [M = Zn, Cu, Co, Ni, Mn], and [n = 0, 1], corresponding to complexes 1–5. The nature of the bond was determined in the solid state and solution using spectral studies (1H-NMR, 13C-NMR, UV-Vis and FT-IR), TGA, EPR, elemental analysis and molar conductivity measurement. Results: All M(II) complexes are 1:1 electrolytes, as illustrated by their molar conductivities. The results demonstrate that all synthesized complexes present a coordination number of six by the bonding of the bidentate ligand via its azomethine nitrogen atoms and carbonyl oxygen atoms, as well as with one nitrate group as a bidentate ligand via two oxygen atoms. The DPPH radical scavenging technique was used to investigate the antioxidant activities of the ligand [L] and the metal complexes. It is clear that the activity increased in M (II) complexes compared to the Schiff base ligand. Complex 5 showed the highest activity, with an excellent activity of 90.4%, while complex 4 showed the lowest. The antibacterial activities of the Schiff base and its complexes have been examined against various pathogenic bacteria to measure their inhibition potential. Complex 2 showed remarkable activity against Gram (+) bacteria and fungi with an MIC value of 8 μg/mL, which is greater than that of the positive controls, oxytetracycline and fluconazole. The catalytic activities of all complexes were examined in the oxidation of aniline, and the results illustrated that all complexes had a 100% selectivity in producing only azobenzene, and complex 4 had the highest activity (91%). Conclusion: The obtained results from this study show that the antioxidant and antibacterial properties of both the Schiff base ligand and its derived complexes are promising, with some demonstrating remarkable activities. Moreover, the catalytic activities and selectivities of the prepared complexes in aniline oxidation are interesting. Full article
(This article belongs to the Special Issue Recent Advance in Transition Metal Complexes and Their Applications II)
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23 pages, 8908 KiB  
Article
Synthesis, Electrochemistry and Density Functional Theory of Osmium(II) Containing Different 2,2′:6′,2″-Terpyridines
by Nandisiwe G. S. Mateyise, Marrigje M. Conradie and Jeanet Conradie
Molecules 2024, 29(21), 5078; https://doi.org/10.3390/molecules29215078 - 27 Oct 2024
Cited by 2 | Viewed by 1845
Abstract
In coordination chemistry, 2,2′:6′,2″-terpyridine is a versatile and extensively studied tridentate ligand. Terpyridine forms stable complexes with a variety of metal ions through coordination sites provided by the three nitrogen atoms in its pyridine rings. This paper presents an electrochemical study on various [...] Read more.
In coordination chemistry, 2,2′:6′,2″-terpyridine is a versatile and extensively studied tridentate ligand. Terpyridine forms stable complexes with a variety of metal ions through coordination sites provided by the three nitrogen atoms in its pyridine rings. This paper presents an electrochemical study on various bis(terpyridine)osmium(II) complexes, addressing the absence of a systematic investigation into their redox behavior. Additionally, a computational chemistry analysis was conducted on these complexes, as well as on eight previously studied osmium(II)-bipyridine and -phenanthroline complexes, to expand both the experimental and theoretical understanding. The experimental redox potentials, Hammett constants, and DFT-calculated energies show linear correlations due to the electron-donating or electron-withdrawing nature of the substituents, as described by the Hammett constants. These substituent effects cause shifts to lower or higher redox potentials, respectively. Full article
(This article belongs to the Special Issue Recent Advance in Transition Metal Complexes and Their Applications II)
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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 - 6 Jul 2024
Cited by 2 | Viewed by 2592
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 Jin Hu and Xuefeng Wang
Molecules 2024, 29(12), 2831; https://doi.org/10.3390/molecules29122831 - 14 Jun 2024
Viewed by 1182
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
Cited by 1 | Viewed by 1620
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, Huiping Xiao, Nannan Wang, Xiaoqi Li, Xinxiong Li, Bing Hu and Xiaoying Huang
Molecules 2024, 29(3), 591; https://doi.org/10.3390/molecules29030591 - 25 Jan 2024
Cited by 1 | Viewed by 1839
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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