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Inorganics, Volume 7, Issue 11 (November 2019)

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Cover Story (view full-size image) A discrete Zn-based metallocycle can be exploited as a platform to self-assemble intertwined [...] Read more.
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Open AccessArticle
Synthesis of Anthraquinones by Iridium-Catalyzed [2 + 2 + 2] Cycloaddition of a 1,2-Bis(propiolyl)benzene Derivative with Alkynes
Inorganics 2019, 7(11), 138; https://doi.org/10.3390/inorganics7110138 - 18 Nov 2019
Abstract
[2 + 2 + 2] cycloaddition of a 1,2-bis(propiolyl)benzene derivative with terminal and internal alkynes takes place in the presence of [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) combined with bis(diphenylphosphino)ethane (DPPE) to give anthraquinones in 42% to 93% yields with a simple experimental procedure. [...] Read more.
[2 + 2 + 2] cycloaddition of a 1,2-bis(propiolyl)benzene derivative with terminal and internal alkynes takes place in the presence of [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) combined with bis(diphenylphosphino)ethane (DPPE) to give anthraquinones in 42% to 93% yields with a simple experimental procedure. A fluorenone derivative can also be synthesized by iridium-catalyzed [2 + 2 + 2] cycloaddition of a benzene-linked ketodiyne with an internal alkyne to give a 94% yield. Full article
(This article belongs to the Special Issue Iridium Complexes)
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Open AccessArticle
A Zn(II) Metallocycle as Platform to Assemble a 1D + 1D → 1D Polyrotaxane via π···π Stacking of an Ancillary Ligand
Inorganics 2019, 7(11), 137; https://doi.org/10.3390/inorganics7110137 - 15 Nov 2019
Abstract
A new [Zn2L2] metallocycle bearing two metal centers that can coordinate ancillary ligands and a pocket suitable to host guest molecules is reported. These two features are exploited by reacting the metallocycle with a pyridine ligand to self-assemble in [...] Read more.
A new [Zn2L2] metallocycle bearing two metal centers that can coordinate ancillary ligands and a pocket suitable to host guest molecules is reported. These two features are exploited by reacting the metallocycle with a pyridine ligand to self-assemble in the solid state an extended intertwined system with the rare 1D + 1D → 1D topology. This interpenetrated architecture is supported by π···π stacking between two pyridine units of two different metallocycles in the pocket of a third metallocycle. Full article
(This article belongs to the Special Issue Recent Advances in Coordination Rings and Cages)
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Open AccessArticle
High-Pressure Synthesis, Crystal Structure, and Photoluminescence Properties of β-Y2B4O9:Eu3+
Inorganics 2019, 7(11), 136; https://doi.org/10.3390/inorganics7110136 - 12 Nov 2019
Abstract
A high-pressure/high-temperature experiment at 7.5 GPa and 1673 K led to the formation of the new compound β-Y2B4O9. In contrast to the already known polymorph α-Y2B4O9, which crystallizes in [...] Read more.
A high-pressure/high-temperature experiment at 7.5 GPa and 1673 K led to the formation of the new compound β-Y2B4O9. In contrast to the already known polymorph α-Y2B4O9, which crystallizes in the space group C2/c, the reported structure could be solved via single-crystal X-ray diffraction in the triclinic space group P 1 ¯ (no. 2) and is isotypic to the already known lanthanide borates β-Dy2B4O9 and β-Gd2B4O9. Furthermore, the photoluminescence of an europium doped sample of β-Y2B4O9:Eu3+ (8%) was investigated. Full article
(This article belongs to the Special Issue Oxido Compounds)
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Open AccessArticle
Theoretical Insights into the Aerobic Hydrogenase Activity of Molybdenum–Copper CO Dehydrogenase
Inorganics 2019, 7(11), 135; https://doi.org/10.3390/inorganics7110135 - 09 Nov 2019
Abstract
The Mo/Cu-dependent CO dehydrogenase from O. carboxidovorans is an enzyme that is able to catalyse CO oxidation to CO 2 ; moreover, it also expresses hydrogenase activity, as it is able to oxidize H 2 . Here, we have studied the dihydrogen oxidation [...] Read more.
The Mo/Cu-dependent CO dehydrogenase from O. carboxidovorans is an enzyme that is able to catalyse CO oxidation to CO 2 ; moreover, it also expresses hydrogenase activity, as it is able to oxidize H 2 . Here, we have studied the dihydrogen oxidation catalysis by this enzyme using QM/MM calculations. Our results indicate that the equatorial oxo ligand of Mo is the best suited base for catalysis. Moreover, extraction of the first proton from H 2 by means of this basic centre leads to the formation of a Mo–OH–Cu I H hydride that allows for the stabilization of the copper hydride, otherwise known to be very unstable. In light of our results, two mechanisms for the hydrogenase activity of the enzyme are proposed. The first reactive channel depends on protonation of the sulphur atom of a Cu-bound cysteine residues, which appears to favour the binding and activation of the substrate. The second reactive channel involves a frustrated Lewis pair, formed by the equatorial oxo group bound to Mo and by the copper centre. In this case, no binding of the hydrogen molecule to the Cu center is observed but once H 2 enters into the active site, it can be split following a low-energy path. Full article
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Open AccessArticle
Towards 99mTc- and Re-Based Multifunctional Silica Platforms for Theranostic Applications
Inorganics 2019, 7(11), 134; https://doi.org/10.3390/inorganics7110134 - 09 Nov 2019
Abstract
Taking advantage of the radiation properties of 99mTc and 186/188Re and the photophysical characteristics of the {M(CO)3}+ moiety (M = Re), we developed a multifunctional silica platform with the theranostic pair 99mTc/Re with high potential for (nano)medical [...] Read more.
Taking advantage of the radiation properties of 99mTc and 186/188Re and the photophysical characteristics of the {M(CO)3}+ moiety (M = Re), we developed a multifunctional silica platform with the theranostic pair 99mTc/Re with high potential for (nano)medical applications. Starting with a general screening to evaluate the most suitable mesoporous silica construct and the development of appropriate chelate systems, multifunctional mesoporous silica microparticles (SBA-15) were synthesized. These particles act as a model towards the synthesis of the corresponding nanoconstructs. The particles can be modified at the external surface with a targeting function and labeled with the {M(CO)3}+ moiety (M = 99mTc, Re) at the pore surface. Thus, a silica platform is realized, whose bioprofile is not altered by the loaded modalities. The described synthetic procedures can be applied to establish a target-specific theranostic nanoplatform, which enables the combination of fluorescence and radio imaging, with the possibility of radio- and chemotherapy. Full article
(This article belongs to the Special Issue Advanced Applications of Technetium Chemistry)
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Open AccessArticle
Cysteine Derivatized 99mTc-Labelled Fatty Acids as β-Oxidation Markers
Inorganics 2019, 7(11), 133; https://doi.org/10.3390/inorganics7110133 - 08 Nov 2019
Abstract
With the aim of developing 99mTc-labeled fatty acids intended for myocardial metabolism imaging we report herein the synthesis and characterization of two novel derivatives of undecanonoic and hexadecanonoic acid that have been functionalized at the ω-site by cysteine through the formation of [...] Read more.
With the aim of developing 99mTc-labeled fatty acids intended for myocardial metabolism imaging we report herein the synthesis and characterization of two novel derivatives of undecanonoic and hexadecanonoic acid that have been functionalized at the ω-site by cysteine through the formation of a thioether bond (Cys–FA11 and Cys–FA16). Equimolar amounts of each ligand and the [NEt4]2[Re(CO)3Br3] precursor generated the respective hexacoordinated neutral complexes in which the ligand coordinated to the metal through the SNO donor system of cysteine. The rhenium complexes were characterized by elemental analysis, IR and NMR spectroscopies. The analogous technetium-99m complexes, 99mTc–Cys–FA11 and 99mTc–Cys–FA16 were prepared by incubation of the ligand with the precursor [99mTc(CO)3(H2O)3]+ (radiochemical yield ≥98%). Their structure was established by comparative HPLC techniques. In vivo studies in mice showed high initial heart uptake for both 99mTc complexes (7.4 ± 0.53 and 7.07 ± 0.73 percentage of injected dose (%ID)/g at 1 min post injection. Rapid clearance (0.60 ± 0.02 %ID/g) was observed for 99mTc–Cys–FA11 while the clearance of the longer fatty acid 99mTc–Cys–FA16 was slower (2.31 ± 0.09 %ID/g at 15 min p.i.). Metabolite analysis study indicated that complexes were catabolized through the β-oxidation process. Full article
(This article belongs to the Special Issue Advanced Applications of Technetium Chemistry)
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Open AccessArticle
Syntheses and Structures of Novel λ33-Phosphanylalumanes Fully Bearing Carbon Substituents and Their Substituent Effects
Inorganics 2019, 7(11), 132; https://doi.org/10.3390/inorganics7110132 - 07 Nov 2019
Abstract
The novel phosphanylalumanes, Al–P single-bond species, fully bearing carbon protecting groups on aluminum and phosphorus atoms, are synthesized by the reactions of aluminum monohalides [(t-Bu)2AlBr and (C6F5)2AlCl·0.5(toluene)] with Mes2PLi. Regarding the [...] Read more.
The novel phosphanylalumanes, Al–P single-bond species, fully bearing carbon protecting groups on aluminum and phosphorus atoms, are synthesized by the reactions of aluminum monohalides [(t-Bu)2AlBr and (C6F5)2AlCl·0.5(toluene)] with Mes2PLi. Regarding the t-Bu system, λ33-phosphanylalumane is obtained. Concerning the C6F5 system, on the other hand, the corresponding LiCl complex, λ44-phosphanylalumane, is obtained. The Al–P bond lengths of C6F5-substituted λ34-, and λ44-derivatives are much shorter than those of the reported λ34-phosphanylalumane derivatives and comparable to that observed for the previously reported λ33-phosphanylalumanes. Theoretical calculations reveal that the binding of the C6F5 groups to Al results in a large contribution of Al and a large s-character in the Al–P bond of phosphanylalumanes. Considering t-Bu-substituted phosphanylalumanes, the Al–P bond lengths reflect the coordination number of Al, showing a longer Al–P bond length in the case of λ4-Al as compared with that of λ3-Al. Combining the structural, spectroscopic, and theoretical results, the t-Bu-substituted λ33-phosphanylalumane has well separated vacant p orbital and lone pairs, which is suitable for reactivity studies. Full article
(This article belongs to the Special Issue Organoaluminum Compounds)
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Open AccessEditorial
Bioinorganic Chemistry of Nickel
Inorganics 2019, 7(11), 131; https://doi.org/10.3390/inorganics7110131 - 30 Oct 2019
Abstract
Following the discovery of the first specific and essential role of nickel in biology in 1975 (the dinuclear active site of the enzyme urease) [...] Full article
(This article belongs to the Special Issue Bioinorganic Chemistry of Nickel)
Open AccessCorrection
Correction: Michaels, H.; et al. Copper Complexes with Tetradentate Ligands for Enhanced Charge Transport in Dye-Sensitized Solar Cells. Inorganics 2018, 6, 53
Inorganics 2019, 7(11), 130; https://doi.org/10.3390/inorganics7110130 - 29 Oct 2019
Abstract
The authors express their sincere apologies to all readers of abovementioned article as mistakes were found upon discussion of the article with colleagues [...] Full article
(This article belongs to the collection Coordination Complexes for Dye-Sensitized Solar Cells (DSCs))
Open AccessArticle
Reaction of Dialumane Incorporating Bulky Eind Groups with Pyridines
Inorganics 2019, 7(11), 129; https://doi.org/10.3390/inorganics7110129 - 25 Oct 2019
Abstract
The reaction of the bulky Eind-based dialumane, (Eind)HAl(μ-H)2AlH(Eind) (1) (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl), with pyridines is described. When 1 was treated with pyridine (Py) in toluene, the Py adduct of aryldihydroalumane, Py→AlH2(Eind) (2 [...] Read more.
The reaction of the bulky Eind-based dialumane, (Eind)HAl(μ-H)2AlH(Eind) (1) (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl), with pyridines is described. When 1 was treated with pyridine (Py) in toluene, the Py adduct of aryldihydroalumane, Py→AlH2(Eind) (2), was initially formed. Then, the hydroalumination of Py took place to yield the Py-bound aryl(1,4-dihydropyrid-1-yl)hydroalumane, Py→AlH(1,4-dihydropyrid-1-yl)(Eind) (3). A similar reaction with a stronger Lewis base, 4-pyrrolidinopyridine (PPy), produced the stable PPy adduct, PPy→AlH2(Eind) (4). The resulting organoaluminum compounds have been fully characterized by NMR spectroscopy as well as X-ray crystallography. The reaction mechanism from 1 to 3 via 2 has been examined by deuterium labeling experiments using (Eind)DAl(μ-D)2AlD(Eind) (1-d4). Full article
(This article belongs to the Special Issue Organoaluminum Compounds)
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Open AccessReview
99mTc Labelling Strategies for the Development of Potential Nitroimidazolic Hypoxia Imaging Agents
Inorganics 2019, 7(11), 128; https://doi.org/10.3390/inorganics7110128 - 23 Oct 2019
Abstract
Technetium-99m has a rich coordination chemistry that offers many possibilities in terms of oxidation states and donor atom sets. Modifications in the structure of the technetium complexes could be very useful for fine tuning the physicochemical and biological properties of potential 99mTc [...] Read more.
Technetium-99m has a rich coordination chemistry that offers many possibilities in terms of oxidation states and donor atom sets. Modifications in the structure of the technetium complexes could be very useful for fine tuning the physicochemical and biological properties of potential 99mTc radiopharmaceuticals. However, systematic study of the influence of the labelling strategy on the “in vitro” and “in vivo” behaviour is necessary for a rational design of radiopharmaceuticals. Herein we present a review of the influence of the Tc complexes’ molecular structure on the biodistribution and the interaction with the biological target of potential nitroimidazolic hypoxia imaging radiopharmaceuticals presented in the literature from 2010 to the present. Comparison with the gold standard [18F]Fluoromisonidazole (FMISO) is also presented. Full article
(This article belongs to the Special Issue Advanced Applications of Technetium Chemistry)
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