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: 31 May 2024 | Viewed by 2067

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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
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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

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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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Published Papers (2 papers)

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Research

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
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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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