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Inorganics, Volume 2, Issue 4 (December 2014) – 11 articles , Pages 540-682

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Communication
Preparation and Cycling Performance of Iron or Iron Oxide Containing Amorphous Al-Li Alloys as Electrodes
Inorganics 2014, 2(4), 674-682; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics2040674 - 12 Dec 2014
Viewed by 2903
Abstract
Crystalline phase transitions cause volume changes, which entails a fast destroying of the electrode. Non-crystalline states may avoid this circumstance. Herein we present structural and electrochemical investigations of pre-lithiated, amorphous Al39Li43Fe13Si5-powders, to be used as [...] Read more.
Crystalline phase transitions cause volume changes, which entails a fast destroying of the electrode. Non-crystalline states may avoid this circumstance. Herein we present structural and electrochemical investigations of pre-lithiated, amorphous Al39Li43Fe13Si5-powders, to be used as electrode material for Li-ion batteries. Powders of master alloys with the compositions Al39Li43Fe13Si5 and Al39Li43Fe13Si5 + 5 mass-% FeO were prepared via ball milling and achieved amorphous/nanocrystalline states after 56 and 21.6 h, respectively. In contrast to their Li-free amorphous pendant Al78Fe13Si9, both powders showed specific capacities of about 400 and 700 Ah/kgAl, respectively, after the third cycle. Full article
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Article
Various Oxygen-Centered Phosphanegold(I) Cluster Cations Formed by Polyoxometalate (POM)-Mediated Clusterization: Effects of POMs and Phosphanes
Inorganics 2014, 2(4), 660-673; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics2040660 - 10 Dec 2014
Cited by 13 | Viewed by 2901
Abstract
Novel phosphanegold(I) cluster cations combined with polyoxometalate (POM) anions, i.e., intercluster compounds, [(Au{P(m-FPh)3})44-O)]2[{(Au{P(m-FPh)3})2 (μ-OH)}2][α-PMo12O40]2·EtOH (1), [(Au{P(m [...] Read more.
Novel phosphanegold(I) cluster cations combined with polyoxometalate (POM) anions, i.e., intercluster compounds, [(Au{P(m-FPh)3})44-O)]2[{(Au{P(m-FPh)3})2 (μ-OH)}2][α-PMo12O40]2·EtOH (1), [(Au{P(m-FPh)3})44-O)]2[α-SiMo12O40]·4H2O (2), [(Au{P(m-MePh)3})44-O)]2[α-SiM12O40] (M = W (3), Mo (4)) and [{(Au {P(p-MePh)3})44-O)}{(Au{P(p-MePh)3})33-O)}][α-PW12O40] (5) were synthesized by POM-mediated clusterization, and unequivocally characterized by elemental analysis, TG/DTA, FT-IR, X-ray crystallography, solid-state CPMAS 31P NMR and solution (1H, 31P{1H}) NMR. Formation of the these gold(I) cluster cations was strongly dependent upon the charge density and acidity of the POMs, and the substituents and substituted positions on the aryl group of triarylphosphane ligands. These gold(I) cluster cations contained various bridged-oxygen atoms such as μ4-O, μ3-O and μ-OH groups. Full article
(This article belongs to the Special Issue Frontiers in Gold Chemistry)
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Article
Coordination Nature of 4-Mercaptoaniline to Sn(II) Ion: Formation of a One Dimensional Coordination Polymer and Its Decomposition to a Mono Nuclear Sn(IV) Complex
Inorganics 2014, 2(4), 652-659; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics2040652 - 08 Dec 2014
Cited by 3 | Viewed by 3202
Abstract
The coordination of the bifunctional ligand 4-mercaptoaniline with aqueo us tin(II) metal ion was studied. A coordination polymer was synthesized when an aqueous solution of SnCl2 was treated with 4-MA. The crystalline material is stable under atmospheric conditions retaining its oxidation state. [...] Read more.
The coordination of the bifunctional ligand 4-mercaptoaniline with aqueo us tin(II) metal ion was studied. A coordination polymer was synthesized when an aqueous solution of SnCl2 was treated with 4-MA. The crystalline material is stable under atmospheric conditions retaining its oxidation state. However, when submerged in a solution saturated with oxygen, the compound oxidizes to a mononuclear tin(IV) complex. Both the compounds were characterized by single crystal X-ray diffraction studies. Although the structure of the tin(IV) complex was previously reported, crystal structure of this compound was redetermined. Full article
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Editorial
Inorganic Fullerene-Like Nanoparticles and Inorganic Nanotubes
Inorganics 2014, 2(4), 649-651; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics2040649 - 28 Nov 2014
Cited by 6 | Viewed by 2517
Abstract
Fullerene-like nanoparticles (inorganic fullerenes; IF) and nanotubes of inorganic layered compounds (inorganic nanotubes; INT) combine low dimensionality and nanosize, enhancing the performance of corresponding bulk counterparts in their already known applications, as well as opening new fields of their own [1]. This issue [...] Read more.
Fullerene-like nanoparticles (inorganic fullerenes; IF) and nanotubes of inorganic layered compounds (inorganic nanotubes; INT) combine low dimensionality and nanosize, enhancing the performance of corresponding bulk counterparts in their already known applications, as well as opening new fields of their own [1]. This issue gathers articles from the diverse area of materials science and is devoted to fullerene-like nanoparticles and nanotubes of layered sulfides and boron nitride and collects the most current results obtained at the interface between fundamental research and engineering.[...] Full article
(This article belongs to the Special Issue Inorganic Fullerene-like Nanoparticles and Inorganic Nanotubes)
Article
Experimental and Theoretical Studies of the Factors Affecting the Cycloplatination of the Chiral Ferrocenylaldimine (SC)-[(η5-C5H5)Fe{(η5-C5H4)–C(H)=N–CH(Me)(C6H5)}]
Inorganics 2014, 2(4), 620-648; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics2040620 - 06 Nov 2014
Cited by 9 | Viewed by 3043
Abstract
The study of the reactivity of the enantiopure ferrocenyl Schiff base (SC)-[FcCH=N–CH(Me)(C6H5)] (1) (Fc = (η5-C5H5)Fe(η5-C5H4)) with cis-[PtCl2(dmso)2 [...] Read more.
The study of the reactivity of the enantiopure ferrocenyl Schiff base (SC)-[FcCH=N–CH(Me)(C6H5)] (1) (Fc = (η5-C5H5)Fe(η5-C5H4)) with cis-[PtCl2(dmso)2] under different experimental conditions is reported. Four different types of chiral Pt(II) have been isolated and characterized. One of them is the enantiomerically pure trans-(SC)-[Pt{κ1-N[FcCH=N–CH(Me)(C6H5)]}Cl2(dmso)] (2a) in which the imine acts as a neutral N-donor ligand; while the other three are the cycloplatinated complexes: [Pt{κ2-C,N [(C6H4)–N=CHFc]}Cl(dmso)] (7a) and the two diastereomers {(Sp,SC) and (Rp,SC)} of [Pt{κ2-C,N[(η5-C5H3)–CH=N–{CH(Me)(C6H5)}]Fe(η5-C5H5)}Cl(dmso)] (8a and 9a, respectively). Isomers 7a-9a, differ in the nature of the metallated carbon atom [CPh (in 7a) or CFc (in 8a and 9a)] or the planar chirality of the 1,2-disubstituted ferrocenyl unit (8a and 9a). Reactions of 7a9a with PPh3 gave [Pt{κ2-C,N[(C6H4)–N=CHFc]}Cl(PPh3)] (in 7b) and the diastereomers (Sp,SC) and (Rp,SC) of [Pt{κ2-C,N[(η5-C5H3)–CH=N–{CH(Me)(C6H5)}] Fe(η5-C5H5)}Cl(PPh3)] (8b and 9b, respectively). Comparative studies of the electrochemical properties and cytotoxic activities on MCF7 and MDA-MB231 breast cancer cell lines of 2a and cycloplatinated complexes 7b-9b are also reported. Theoretical studies based on DFT calculations have also been carried out in order to rationalize the results obtained from the cycloplatination of 1, the stability of the Pt(II) complexes and their electrochemical properties. Full article
(This article belongs to the Special Issue Organoplatinum Complexes)
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Article
High-Energy-Low-Temperature Technologies for the Synthesis of Nanoparticles: Microwaves and High Pressure
Inorganics 2014, 2(4), 606-619; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics2040606 - 06 Nov 2014
Cited by 19 | Viewed by 3326
Abstract
Microwave Solvothermal Synthesis (MSS) is a chemical technology, where apart from possible effects of microwaves on the chemical reaction paths, microwave heating allows the precise planning of a time-temperature schedule, as well as to achieve high super-saturation of the reagents uniformly in the [...] Read more.
Microwave Solvothermal Synthesis (MSS) is a chemical technology, where apart from possible effects of microwaves on the chemical reaction paths, microwave heating allows the precise planning of a time-temperature schedule, as well as to achieve high super-saturation of the reagents uniformly in the reactor vessel. Thus, MSS is suitable for production of nanoparticles with small grain size distribution and a high degree of crystallinity. A further advantage of the technology is a much lower synthesis temperature than for gas phase, plasma or sol-gel technologies. New reactors have been developed to exploit these advantages of the MSS technology of nanoparticles synthesis and to scale up the production rate. Reactor design and realization has been shown to be decisive and critical for the control of the MSS technology. Examples of oxidic and phosphatic nanoparticles synthesis have been reported. Full article
(This article belongs to the Special Issue Inorganic Syntheses Assisted by Microwave Heating)
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Article
A Hydrido η1-Alkynyl Diplatinum Complex Obtained from a Phosphinito Phosphanido Complex and Trimethylsilylacetylene
Inorganics 2014, 2(4), 591-605; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics2040591 - 31 Oct 2014
Cited by 6 | Viewed by 2601
Abstract
The reaction of (trimethylsilyl)acetylene with the phosphinito phosphanido Pt(I) complex [(PHCy2)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt-Pt) (1) results in the protonation of the Pt-Pt bond with the formation of the bridging [...] Read more.
The reaction of (trimethylsilyl)acetylene with the phosphinito phosphanido Pt(I) complex [(PHCy2)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt-Pt) (1) results in the protonation of the Pt-Pt bond with the formation of the bridging hydride complex [(PHCy2)(Me3SiC≡C)Pt(μ-PCy2)(μ-H) Pt(PHCy2){κP-P(O)Cy2}](Pt-Pt) (2), which was characterized by spectroscopic, spectrometric and XRD analyses. Complex 2 exhibits in the solid state at 77 K a long-lived, weak, orange emission assigned as metal-metal to ligand charge transfer (MMLCT) (L = alkynyl) due to the presence of a very short Pt···Pt distance [2.8209(2) Å]. Reaction of 2 with etherate HBF4 results in the selective protonation of the phosphinito ligand to afford the species [(PHCy2)(Me3SiC≡C)Pt(μ-PCy2)(μ-H) Pt(PHCy2){κP-P(OH)Cy2}](Pt-Pt)[BF4] ([3]BF4). Full article
(This article belongs to the Special Issue Organoplatinum Complexes)
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Article
Attachment of Luminescent Neutral “Pt(pq)(C≡CtBu)” Units to Di and Tri N-Donor Connecting Ligands: Solution Behavior and Photophysical Properties
Inorganics 2014, 2(4), 565-590; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics2040565 - 31 Oct 2014
Cited by 1 | Viewed by 2835
Abstract
Binuclear derivatives [{Pt(pq)(C≡CtBu)}2(μ-L)] (1a5a), containing a series of dinitrogen linker ligands and the trinuclear [{Pt(pq)(C≡CtBu)}3(μ-L)] (6a) [L = μ-1,3,5-tris(pyridine-4-ylethynyl)benzene], formed by bridge-splitting reactions with [Pt(pq)(μ-κCα2 [...] Read more.
Binuclear derivatives [{Pt(pq)(C≡CtBu)}2(μ-L)] (1a5a), containing a series of dinitrogen linker ligands and the trinuclear [{Pt(pq)(C≡CtBu)}3(μ-L)] (6a) [L = μ-1,3,5-tris(pyridine-4-ylethynyl)benzene], formed by bridge-splitting reactions with [Pt(pq)(μ-κCα2-C≡CtBu)]2 (Pt-1), are reported. The complexes are characterized by a combination of 1H NMR spectroscopy, mass spectrometry and X-ray crystallography (2a and 4a). 1H NMR proves the existence of a dynamic equilibrium in solution between the diplatinum complexes (species a), the corresponding mononuclear complex with terminal N-donor ligands (species b), the starting material (Pt-1) and the free ligand (L). The effects of concentration, temperature and solvent properties on the equilibrium have been studied. The optical properties of these systems have been investigated by UV-visible absorption and emission spectroscopies in solid state and in solution, and the nature of the transitions and the excited state analyzed by theoretical calculations on 2a. Full article
(This article belongs to the Special Issue Organoplatinum Complexes)
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Article
Noble-Metal Chalcogenide Nanotubes
Inorganics 2014, 2(4), 556-564; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics2040556 - 24 Oct 2014
Cited by 4 | Viewed by 3261
Abstract
We explore the stability and the electronic properties of hypothetical noble-metal chalcogenide nanotubes PtS2, PtSe2, PdS2 and PdSe2 by means of density functional theory calculations. Our findings show that the strain energy decreases inverse quadratically with the [...] Read more.
We explore the stability and the electronic properties of hypothetical noble-metal chalcogenide nanotubes PtS2, PtSe2, PdS2 and PdSe2 by means of density functional theory calculations. Our findings show that the strain energy decreases inverse quadratically with the tube diameter, as is typical for other nanotubes. Moreover, the strain energy is independent of the tube chirality and converges towards the same value for large diameters. The band-structure calculations show that all noble-metal chalcogenide nanotubes are indirect band gap semiconductors. The corresponding band gaps increase with the nanotube diameter rapidly approaching the respective pristine 2D monolayer limit. Full article
(This article belongs to the Special Issue Inorganic Fullerene-like Nanoparticles and Inorganic Nanotubes)
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Editorial
Innovative Inorganic Synthesis
Inorganics 2014, 2(4), 552-555; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics2040552 - 17 Oct 2014
Viewed by 2444
Abstract
I am delighted to introduce this Special Issue of Inorganics; the first themed issue of the journal and one dedicated to Innovative Inorganic Synthesis. [...] Full article
(This article belongs to the Special Issue Innovative Inorganic Synthesis)
Article
Reactivity of Mononuclear and Dinuclear Gold(I) Amidinate Complexes with CS2 and CsBr3
Inorganics 2014, 2(4), 540-551; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics2040540 - 08 Oct 2014
Cited by 6 | Viewed by 3206
Abstract
To probe the reactivity of gold-nitrogen bonds, we have examined the insertion chemistry with carbon disulfide (CS2) as well as oxidation with cesium tribromide (CsBr3) with Au(I) amidinate complexes. The reaction of Ph3PAuCl with Na[(2,6-Me2C [...] Read more.
To probe the reactivity of gold-nitrogen bonds, we have examined the insertion chemistry with carbon disulfide (CS2) as well as oxidation with cesium tribromide (CsBr3) with Au(I) amidinate complexes. The reaction of Ph3PAuCl with Na[(2,6-Me2C6H3N)2C(H)] yields the mononuclear, two-coordinate gold(I) complex, Ph3PAu[κ1-(2,6-Me2C6H3N)2C(H)], 1. The reactivity of 1 with CS2 produced the mononuclear Au(I) compound, Ph3PAu{κ1-S2C[(2,6-Me2C6H3N)2C(H)]}, 2. In the case of CsBr3 the previously reported dinuclear Au(I) complex, Au[(2,6-Me2C6H3N)2C(H)]2, 3, was isolated with formation of Ph3PBr2. We also compared the reactivity of CS2 and CsBr3 with 3. Carbon disulfide insertion with 3 produces a dimeric product, Aun[CS2(2,6-Me2C6H3NC(H)=NC6H3Me2)]n, 4, featuring a dinuclear core with linking aurophilic interactions, making it appear polymeric in the solid state. When CsBr3 is reacted with 3 the Au(II,II) product is obtained, Au2[(2,6-Me2C6H3N)2C(H)]2(Br)2, 5. Full article
(This article belongs to the Special Issue Frontiers in Gold Chemistry)
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