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Inorganics, Volume 8, Issue 12 (December 2020) – 6 articles

Cover Story (view full-size image): CaTiO3, SrTiO3, and BaTiO3 films of 1 nm were deposited onto MgAl2O4 via atomic layer deposition and studied as catalyst supports for Ni. Scanning transmission electron microscopy demonstrated that both the Ni and the perovskites uniformly covered the surface of the support upon oxidation, but Ni particles formed following a reduction at 1073 K. When compared to Ni/MgAl2O4, the perovskite-containing catalysts required higher temperatures for Ni reduction. Equilibrium constants for Ni oxidation determined from coulometric titration indicated that the oxidation of Ni shifted to lower PO2 on the perovskite-containing materials. Based on Ni equilibrium constants, Ni interactions are strongest with CaTiO3, followed by SrTiO3 and BaTiO3. View this paper
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Open AccessArticle
A Thermodynamic Investigation of Ni on Thin-Film Titanates (ATiO3)
Inorganics 2020, 8(12), 69; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8120069 - 11 Dec 2020
Viewed by 596
Abstract
Thin, ~1-nm films of CaTiO3, SrTiO3, and BaTiO3 were deposited onto MgAl2O4 by Atomic Layer Deposition (ALD) and then studied as catalyst supports for ~5 wt % of Ni that was added to the perovskite [...] Read more.
Thin, ~1-nm films of CaTiO3, SrTiO3, and BaTiO3 were deposited onto MgAl2O4 by Atomic Layer Deposition (ALD) and then studied as catalyst supports for ~5 wt % of Ni that was added to the perovskite thin films by Atomic Layer Deposition. Scanning Transmission Electron Microscopy demonstrated that both the Ni and the perovskites uniformly covered the surface of the support following oxidation at 1073 K, even after redox cycling, but large Ni particles formed following a reduction at 1073 K. When compared to Ni/MgAl2O4, the perovskite-containing catalysts required significantly higher temperatures for Ni reduction. Equilibrium constants for Ni oxidation, as determined from Coulometric Titration, indicated that the oxidation of Ni shifted to lower PO2 on the perovskite-containing materials. Based on Ni equilibrium constants, Ni interactions are strongest with CaTiO3, followed by SrTiO3 and BaTiO3. The shift in the equilibrium constant was shown to cause reversible deactivation of the Ni/CaTiO3/MgAl2O4 catalyst for CO2 reforming of CH4 at high CO2 pressures, due to the oxidation of the Ni. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Open AccessReview
Ferrocenyl Migrations and Molecular Rearrangements: The Significance of Electronic Charge Delocalization
Inorganics 2020, 8(12), 68; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8120068 - 11 Dec 2020
Cited by 1 | Viewed by 432
Abstract
The enhanced stabilization of a carbocationic site adjacent to a ferrocenyl moiety was recognized within a few years of the discovery of sandwich compounds. While a detailed understanding of the phenomenon was the subject of some early debate, researchers soon took advantage of [...] Read more.
The enhanced stabilization of a carbocationic site adjacent to a ferrocenyl moiety was recognized within a few years of the discovery of sandwich compounds. While a detailed understanding of the phenomenon was the subject of some early debate, researchers soon took advantage of it to control the ease and direction of a wide range of molecular rearrangements. We, here, discuss the progress in this area from the pioneering studies of the 1960s, to more recent applications in chromatography and analytical detection techniques, and currently in the realm of bioactive organometallic complexes. Several classic reactions involving ferrocenyl migrations, such as the pinacol, Wolff, Beckmann, and Curtius, are discussed, as well as the influence of the ferrocenyl substituent on the mechanisms of the Nazarov, Meyer-Schuster, benzoin, and Stevens rearrangements. The preparation and isomerizations of ferrocenyl-stabilized vinyl cations and vinylcyclopropenes, together with the specific cyclization of acetylcyclopentadienyl-metal derivatives to form 1,3,5-substituted benzenes, demonstrate the versatility and generality of this approach. Full article
(This article belongs to the Special Issue Ferrocene and Its Derivatives. Memories of the Future)
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Open AccessArticle
Kinetic Studies of Sodium and Metforminium Decavanadates Decomposition and In Vitro Cytotoxicity and Insulin- Like Activity
Inorganics 2020, 8(12), 67; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8120067 - 08 Dec 2020
Viewed by 531
Abstract
The kinetics of the decomposition of 0.5 and 1.0 mM sodium decavanadate (NaDeca) and metforminium decavanadate (MetfDeca) solutions were studied by 51V NMR in Dulbecco’s modified Eagle’s medium (DMEM) medium (pH 7.4) at 25 °C. The results showed that decomposition products are [...] Read more.
The kinetics of the decomposition of 0.5 and 1.0 mM sodium decavanadate (NaDeca) and metforminium decavanadate (MetfDeca) solutions were studied by 51V NMR in Dulbecco’s modified Eagle’s medium (DMEM) medium (pH 7.4) at 25 °C. The results showed that decomposition products are orthovanadate [H2VO4] (V1) and metavanadate species like [H2V2O7]2− (V2), [V4O12]4− (V4) and [V5O15]5− (V5) for both compounds. The calculated half-life times of the decomposition reaction were 9 and 11 h for NaDeca and MetfDeca, respectively, at 1 mM concentration. The hydrolysis products that presented the highest rate constants were V1 and V4 for both compounds. Cytotoxic activity studies using non-tumorigenic HEK293 cell line and human liver cancer HEPG2 cells showed that decavanadates compounds exhibit selectivity action toward HEPG2 cells after 24 h. The effect of vanadium compounds (8–30 μM concentration) on the protein expression of AKT and AMPK were investigated in HEPG2 cell lines, showing that NaDeca and MetfDeca compounds exhibit a dose-dependence increase in phosphorylated AKT. Additionally, NaDeca at 30 µM concentration stimulated the glucose cell uptake moderately (62%) in 3T3-L1 adipocytes. Finally, an insulin release assay in βTC-6 cells (30 µM concentration) showed that sodium orthovanadate (MetV) and MetfDeca enhanced insulin release by 0.7 and 1-fold, respectively. Full article
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Open AccessReview
Lanthanide-Based Single-Molecule Magnets Derived from Schiff Base Ligands of Salicylaldehyde Derivatives
Inorganics 2020, 8(12), 66; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8120066 - 04 Dec 2020
Viewed by 638
Abstract
The breakthrough in Ln(III)-based SMMs with Schiff base ligands have been occurred for the last decade on account of their magnetic behavior, anisotropy and relaxation pathways. Herein, we review the synthetic strategy, from a structural point of view and magnetic properties of mono, [...] Read more.
The breakthrough in Ln(III)-based SMMs with Schiff base ligands have been occurred for the last decade on account of their magnetic behavior, anisotropy and relaxation pathways. Herein, we review the synthetic strategy, from a structural point of view and magnetic properties of mono, di, tri and polynuclear Ln(III)-based single-molecule magnets mainly with Schiff bases of Salicylaldehyde origin. Special attention has been given to some important breakthroughs that are changing the perspective of this field with a special emphasis on slow magnetic relaxation. An overview of 50 Ln(III)-Schiff base complexes with SMM behavior, covering the period 2008–2020, which have been critical in understanding the magnetic interactions between the Ln(III)-centers, are presented and discussed in detail. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Open AccessArticle
CuII Complexes and Coordination Polymers with Pyridine or Pyrazine Amides and Amino Benzamides—Structures and EPR Patterns
Inorganics 2020, 8(12), 65; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8120065 - 01 Dec 2020
Viewed by 487
Abstract
Isonicotine amide, picoline amide, pyrazine 2-amide, 2- and 4-amino benzamides and various CuII salts were used to target CuII complexes of these ligands alongside with 1D and 2D coordination polymers. Under the criterion of obtaining crystalline and single phased materials a [...] Read more.
Isonicotine amide, picoline amide, pyrazine 2-amide, 2- and 4-amino benzamides and various CuII salts were used to target CuII complexes of these ligands alongside with 1D and 2D coordination polymers. Under the criterion of obtaining crystalline and single phased materials a number of new compounds were reliably reproduced. Remarkably, for some of these compounds the ideal Cu:ligand ratio of the starting materials turned out to be very different from Cu:ligand ratio in the products. Crystal and molecular structures from single-crystal XRD were obtained for all new compounds; phase purity was checked using powder XRD. We observed exclusively the Oamide and not the NH2amide function binding to CuII. In most of the cases; this occurred in chelates with the second pyridine, pyrazine or aminophenyl N function. µ-O,N ditopic bridging was frequently observed for the N = pyridine, pyrazine or aminophenyl functions, but not exclusively. The geometry around CuII in these compounds was very often axially elongated octahedral or square pyramidal. X-band EPR spectra of powder samples revealed various spectral symmetry patterns ranging from axial over rhombic to inverse axial. Although the EPR spectra cannot be unequivocally correlated to the observed geometry of CuII in the solid state structures, the EPR patterns can help to support assumed structures as shown for the compound [Cu(Ina)2Br2] (Ina = isonicotine amide). As UV-vis absorption spectroscopy and magnetic measurement in the solid can also be roughly correlated to the surrounding of CuII, we suggest the combination of EPR, UV-vis spectroscopy and magnetic measurements to elucidate possible structures of CuII compounds with such ligands. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Open AccessCommunication
Silver Cyanoguanidine Nitrate Hydrate: Ag(C2N4H4)NO3·½ H2O, a Cyanoguanidine Compound Coordinating by an Inner Nitrogen Atom
Inorganics 2020, 8(12), 64; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8120064 - 24 Nov 2020
Viewed by 568
Abstract
Silver(I) cyanoguanidine nitrate hydrate, Ag(C2N4H4)NO3·½H2O, was synthesized as the first cyanoguanidine solid-state complex in which monovalent Ag is coordinated through inner nitrogen N atoms. Its structure was characterized by single-crystal X-ray diffraction, crystallizing [...] Read more.
Silver(I) cyanoguanidine nitrate hydrate, Ag(C2N4H4)NO3·½H2O, was synthesized as the first cyanoguanidine solid-state complex in which monovalent Ag is coordinated through inner nitrogen N atoms. Its structure was characterized by single-crystal X-ray diffraction, crystallizing in the acentric orthorhombic space group P21212 with a = 10.670(3) Å, b = 18.236(5) Å, and c = 3.5078(9) Å. The differing chemical bondings of Ag(C2N4H4)NO3·½H2O and Ag(C2N4H4)3NO3 were compared on the basis of first-principle calculations. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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