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Inorganics
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Metal Complexes with N-donor Ligands, 2nd Edition
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Metal Complexes with N-donor Ligands, 2nd Edition

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

Deadline for manuscript submissions: closed (31 October 2024) | Viewed by 6407

Special Issue Editor

Dr. László Kótai

E-Mail Website
Guest Editor
Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar Tudósok Körútja 2, H-1117 Budapest, Hungary
Interests: coordination chemistry; redox reactions; inorganic synthesis; ammines; oxometallate salts; pyridine complexes; urea complexes; thermal analysis; spectroscopy; structure determination
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues, 

Complexes of metals with N-base ligands like ammonia, amines, urea derivatives, or N-heterocycles are a highly important class of compounds in chemistry, biochemistry, and material science. Many enzymes comprise these kinds of metal complexes. Coordination chemistry of metal complexes with N-bases, including structural features and ligand–central atom or ligand–anion interactions in the solid or solution phase, offers facile routes to prepare and study such industrially important materials. For instance, the interaction of oxidizing anions with reducing N-base ligands within these complex compounds can result in mixed oxides of a nanometric size that can be used as catalysts in various technologically important reactions such as CO2 reduction, Fischer–Tropsch synthesis, CO oxidation, etc.   

Given the success of the first edition of this Special Issue, a second volume was launched, seeking to gather original research papers and comprehensive review articles focusing on the chemistry of metal complexes containing N-base ligands (ammonia, amines, urea and pyridine, or other N-heterocycle derivatives) and their relevance to science and industry.  

Dr. László Kótai
Guest Editor

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. Inorganics is an international peer-reviewed open access monthly 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

  • ammonia complexes
  • pyridine complexes
  • heterocyclic N-base complexes
  • transition and non-transition metal complexes
  • complex structures
  • redox reactions of ligands in complexes

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Related Special Issue

Published Papers (5 papers)

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Research

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28 pages, 5753 KiB  
Article
Ni(II) and Cu(II) Ion Coordination by the Novel (2E,2′E)-N,N′-(2-Hydroxypropane-1,3-diyl)bis[(2-hydroxyimino)propanamide] Ligand in the Solid State and in Aqueous Medium
by Igor Vasyl Nikolayenko, Carla Bazzicalupi, Thomas-John Theron and Craig Grimmer
Inorganics 2024, 12(12), 330; https://doi.org/10.3390/inorganics12120330 - 17 Dec 2024
Viewed by 472
Abstract
In the process of a systematic study of the bis-chelate oxime-amide ligands with different polymethylene spacers and their transition metal complexes, two new Ni(II) and Cu(II) complexes of the mhiea2poh ligand have been isolated, and their molecular and crystal structures [...] Read more.
In the process of a systematic study of the bis-chelate oxime-amide ligands with different polymethylene spacers and their transition metal complexes, two new Ni(II) and Cu(II) complexes of the mhiea2poh ligand have been isolated, and their molecular and crystal structures determined by single crystal X-ray diffraction. Potentiometric titrations were performed on a range of aqueous solutions in both systems, which allowed the identification of various complex species and afforded their stability constants. ESR spectra of samples with optimised concentrations of complexes in Cu(II)–L–H system were recorded. A distinguishing feature of both systems is the dimerization of anionic pseudo-macrocyclic complexes. The latter is caused either by centrosymmetric hydrogen bonding of the hydroxy group on the propane spacer to the oximato oxygen of the opposing unit or by back-to-back π-stacking of planar complex units. ESR measurements indicated likely coupling of Cu-Cu paramagnetic centres in the dimers. Full article
(This article belongs to the Special Issue Metal Complexes with N-donor Ligands, 2nd Edition)
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21 pages, 7847 KiB  
Article
Unusual Metal–organic Multicomponent Ni(II) and Mononuclear Zn(II) Compounds Involving Pyridine dicarboxylates: Supramolecular Assemblies and Theoretical Studies
by Kamal K. Dutta, Pranay Sharma, Subham Banik, Rosa M. Gomila, Antonio Frontera, Miquel Barcelo-Oliver and Manjit K. Bhattacharyya
Inorganics 2024, 12(10), 267; https://doi.org/10.3390/inorganics12100267 - 14 Oct 2024
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Abstract
In the present work, we reported the synthesis and characterization [single crystal X-ray diffraction technique, spectroscopic, etc.] of two new Ni(II) and Zn(II) coordination compounds, viz. [Ni(2,6-PDC)2]2[Ni(en)2(H2O)2]2[Ni(en)(H2O)4 [...] Read more.
In the present work, we reported the synthesis and characterization [single crystal X-ray diffraction technique, spectroscopic, etc.] of two new Ni(II) and Zn(II) coordination compounds, viz. [Ni(2,6-PDC)2]2[Ni(en)2(H2O)2]2[Ni(en)(H2O)4]·4H2O (1) and [Zn(2,6-PDC)(Hdmpz)2] (2) (where 2,6-PDC = 2,6-pyridinedicarboxylate, en = ethylene-1,2-diamine, and Hdmpz = 3,5-dimethyl pyrazole). Compound 1 is found to crystallize as a multicomponent Ni(II) compound with five discrete complex moieties, whereas compound 2 is isolated as a mononuclear Zn(II) compound. A deep analysis of the crystal structure of 1 unfolds unusual dual enclathration of guest complex cationic moieties within the supramolecular host cavity stabilized by anion–π, π-stacking, N–H⋯O, C–H⋯O, and O–H⋯O hydrogen bonding interactions. Again, the crystal structure of compound 2 is stabilized by the presence of unconventional C–H⋯π(chelate ring) interactions along with C–H⋯O, C–H⋯N hydrogen bonding, π-stacking, and C–H⋯π(pyridyl) interactions. These non-covalent interactions were further studied theoretically using density functional theory (DFT) calculations, molecular electrostatic potential (MEP) surfaces, non-covalent interaction (NCI) plot index, and quantum theory of atoms in molecules (QTAIM) computational tools. The computational study displays that π-stacking or H bonds greatly tune the directionality of compound 1, although non-directional electrostatic forces dominate energetically. For compound 2, a combined QTAIM/NCI plot analysis confirms the presence of unconventional C–H⋯π(chelate ring) interactions along with other weak interactions obtained from the crystal structure analysis. Further, the individual energy contributions of these weak yet significant non-covalent interactions have also been determined computationally. Full article
(This article belongs to the Special Issue Metal Complexes with N-donor Ligands, 2nd Edition)
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28 pages, 8640 KiB  
Article
Insight into the Structure and Redox Chemistry of [Carbonatotetraamminecobalt(III)] Permanganate and Its Monohydrate as Co-Mn-Oxide Catalyst Precursors of the Fischer-Tropsch Synthesis
by Kende Attila Béres, Zsolt Dürvanger, Zoltán Homonnay, Laura Bereczki, Berta Barta Holló, Attila Farkas, Vladimir M. Petruševski and László Kótai
Inorganics 2024, 12(4), 94; https://doi.org/10.3390/inorganics12040094 - 22 Mar 2024
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Abstract
[Carbonatotetraamminecobalt(III)] permanganate monohydrate was synthesized first in the metathesis reaction of [Co(NH3)4CO3]NO3 and NaMnO4 in aqueous solution. Its thermal dehydration at 100 °C resulted in phase-pure [Co(NH3)4CO3]MnO4 (compound [...] Read more.
[Carbonatotetraamminecobalt(III)] permanganate monohydrate was synthesized first in the metathesis reaction of [Co(NH3)4CO3]NO3 and NaMnO4 in aqueous solution. Its thermal dehydration at 100 °C resulted in phase-pure [Co(NH3)4CO3]MnO4 (compound 1). Compounds 1 and 2 (i.e., the hydrated form) were studied with IR, far-IR, and low-temperature Raman spectroscopies, and their vibrational modes were assigned. The lattice parameters were determined by powder X-ray diffraction (PXRD) and single crystal X-ray diffraction (SXRD) methods for the triclinic and orthorhombic compounds 1 and 2, respectively. The detailed structure of compound 2 was determined, and the role of hydrogen bonds in the structural motifs was clarified. UV studies on compounds 1 and 2 showed the distortion of the octahedral geometry of the complex cation during dehydration because of the partial loss of the hydrogen bonds between the crystal water and the ligands of the complex cation. The thermal decomposition consists of a solid phase quasi-intramolecular redox reaction between the ammonia ligands and permanganate anions with the formation of ammonia oxidation products (H2O, NO, N2O, and CO2). The solid phase reaction product is amorphous cobalt manganese oxide containing ammonium, carbonate (and nitrate) anions. The temperature-controlled thermal decomposition of compound 2 in toluene at 110 °C showed that one of the decomposition intermediates is ammonium nitrate. The decomposition intermediates are transformed into Co1.5Mn1.5O4 spinel with MnCo2O4 structure upon further heating. Solid compound 2 gave the spinel at 500 °C both in an inert and air atmosphere, whereas the sample pre-treated in toluene at 110 °C without and with the removal of ammonium nitrate by aqueous washing, gave the spinel already at 300 and 400 °C, respectively. The molten NH4NO3 is a medium to start spinel crystallization, but its decomposition stops further crystal growth of the spinel phase. By this procedure, the particle size of the spinel product as low as ~4.0 nm could be achieved for the treatments at 300 and 400 °C, and it increased only to 5.7 nm at 500 °C. The nano-sized mixed cobalt manganese oxides are potential candidates as Fischer-Tropsch catalysts. Full article
(This article belongs to the Special Issue Metal Complexes with N-donor Ligands, 2nd Edition)
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14 pages, 3896 KiB  
Article
Two Isomers of a Novel Ag(I) Complex with Pyrazole-Type Ligand—Synthesis, Structural, Thermal, and Antioxidative Characterization
by Nikola D. Radnović, Nađa Štetin, Mirjana M. Radanović, Ivana Đ. Borišev, Marko V. Rodić, Željko K. Jaćimović and Berta Barta Holló
Inorganics 2024, 12(1), 4; https://doi.org/10.3390/inorganics12010004 - 21 Dec 2023
Cited by 1 | Viewed by 1750
Abstract
The synthesis of the first Ag(I) complexes with ethyl-5-amino-1-methyl-1H-pyrazole-4-carboxylate (L) is presented. The reaction of AgClO4 with the ligand in a molar ratio of 1:1 gives a bis(ligand) complex [AgL2]ClO4 (1) in the presence [...] Read more.
The synthesis of the first Ag(I) complexes with ethyl-5-amino-1-methyl-1H-pyrazole-4-carboxylate (L) is presented. The reaction of AgClO4 with the ligand in a molar ratio of 1:1 gives a bis(ligand) complex [AgL2]ClO4 (1) in the presence of 4-formylbenzonitrile, monoperiodic polymer {[AgL2]ClO4}n (2). Characterization involved IR spectroscopy, conductometric measurements, thermogravimetric analysis, antioxidant tests, powder, and single crystal X-ray diffraction. Structural analysis revealed ligand coordination in a monodentate manner through the nitrogen atom of the pyrazole ring in both complexes. Complex 1 displayed a linear coordination environment for Ag(I), whereas, in complex 2, square-planar coordination was achieved with the additional involvement of two oxygen atoms from bridging perchlorate anions. Notably, the thermal properties of both isomers are found to be nearly identical. The significant antioxidant activity of the isomer with a reverse-oriented pyrazole-type ligand suggests its potential relevance in biological studies. Full article
(This article belongs to the Special Issue Metal Complexes with N-donor Ligands, 2nd Edition)
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Review

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15 pages, 2913 KiB  
Review
Late Transition Metal Olefin Polymerization Catalysts Derived from 8-Arylnaphthylamines
by Zonglin Qiu, Wenyan Wang, Handou Zheng, Dengfei Wang, Xinglong Zhao, Guangshui Tu, Jiahao Yang and Haiyang Gao
Inorganics 2024, 12(11), 277; https://doi.org/10.3390/inorganics12110277 - 28 Oct 2024
Viewed by 977
Abstract
Late transition metal catalysts represent a significant class of olefin polymerization catalysts that have played an essential role in advancing the polyolefin industry owing to their highly tunable ligands and low oxophilicity. A key feature for the design of late transition metal catalysts [...] Read more.
Late transition metal catalysts represent a significant class of olefin polymerization catalysts that have played an essential role in advancing the polyolefin industry owing to their highly tunable ligands and low oxophilicity. A key feature for the design of late transition metal catalysts lies in the steric bulk of the o-aryl substituents. Bulky 8-arylnaphthylamines have emerged as a promising aniline candidate for conducting high-performance catalysts by introducing axially steric hindrance around the metal center. This review focuses on late transition metal (Ni, Pd, Fe) catalysts derived from 8-arylnaphthylamines, surveying their synthesis, structural features, and catalytic applications in olefin (co)polymerizations. Additionally, the relationship between catalyst structure and catalytic performance is discussed, highlighting how these unique ligand systems influence polymerization activity, molecular weight, and polymer branching. Full article
(This article belongs to the Special Issue Metal Complexes with N-donor Ligands, 2nd Edition)
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