Traversing the Boundaries of Inorganic Chemistry

A special issue of Inorganics (ISSN 2304-6740).

Deadline for manuscript submissions: closed (15 June 2016) | Viewed by 67266

Special Issue Editor

School of Chemistry, University of Glasgow, University Avenue, Glasgow G12 8QQ, UK
Interests: nitrides; chalcogenides; carbides; hydrides; synthesis; structure; solid-state chemistry; materials chemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Inorganic Chemistry is one of the fundamental foundations upon which the chemical sciences are built, and the discipline remains a lynchpin of modern chemistry. Not only does inorganic chemistry embrace the meaning behind function and reactivity of combinations of most of the members of the periodic table, but also it provides a footing for studies of materials, catalysts, drugs, fuels, and industrial chemicals. Arguably, the role, reach, and importance of inorganics in society have never been as great as they are at present. Adventurous research at the heart of and at the extremes of Inorganic Chemistry is vital to further advances.

This Special Issue aims to collect high quality papers (original research articles or comprehensive review papers) in Inorganic Chemistry research fields. Highly experienced practitioners from various fields within the journal’s scope are welcome to contribute papers, highlighting the latest developments in their research areas, or detailed summaries of their own work done thus far.

Potential topics include, but are not limited to:

  • synthesis and characterization of inorganic compounds, complexes, and materials
  • structure and bonding in inorganic molecular and solid state compounds
  • spectroscopic and magnetic properties of inorganic compounds
  • chemical reactivity, physical properties, and applications of inorganic compounds and materials
  • mechanisms of inorganic reactions
  • organometallic compounds
  • inorganic cluster chemistry
  • heterogeneous and homogeneous catalytic reactions promoted by inorganic compounds
  • thermodynamics and kinetics of significant new and known inorganic compounds
  • supramolecular systems and coordination polymers
  • bio-inorganic chemistry and applications of inorganic compounds in biological systems and medicine
  • environmental and sustainable energy applications of inorganic compounds and materials

Prof. Dr. Duncan H. Gregory
Guest Editor

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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

  • Mechanisms of inorganic reactions
  • Organometallic chemistry
  • Solid state compounds
  • Chemical bonding theory
  • Theoretical and computational studies
  • Bioinorganic chemistry
  • Electronic and magnetic properties
  • Main group chemistry
  • Transition metal cluster chemistry
  • Environmental and sustainable energy applications

Published Papers (11 papers)

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Research

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1234 KiB  
Article
The Role of Anisotropic Exchange in Single Molecule Magnets: A CASSCF/NEVPT2 Study of the Fe4 SMM Building Block [Fe2(OCH3)2(dbm)4] Dimer
by Alessandro Lunghi and Federico Totti
Inorganics 2016, 4(4), 28; https://doi.org/10.3390/inorganics4040028 - 22 Sep 2016
Cited by 15 | Viewed by 5964
Abstract
The rationalisation of single molecule magnets’ (SMMs) magnetic properties by quantum mechanical approaches represents a major task in the field of the Molecular Magnetism. The fundamental interpretative key of molecular magnetism is the phenomenological Spin Hamiltonian and the understanding of the role of [...] Read more.
The rationalisation of single molecule magnets’ (SMMs) magnetic properties by quantum mechanical approaches represents a major task in the field of the Molecular Magnetism. The fundamental interpretative key of molecular magnetism is the phenomenological Spin Hamiltonian and the understanding of the role of its different terms by electronic structure calculations is expected to steer the rational design of new and more performing SMMs. This paper deals with the ab initio calculation of isotropic and anisotropic exchange contributions in the Fe(III) dimer [Fe 2 (OCH 3 ) 2 (dbm) 4 ]. This system represents the building block of one of the most studied Single Molecule Magnets ([Fe 4 RC(CH 2 O) 3 ) 2 (dpm) 6 ] where R can be an aliphatic chain or a phenyl group just to name the most common functionalization groups) and its relatively reduced size allows the use of a high computational level of theory. Calculations were performed using CASSCF and NEVPT2 approaches on the X-ray geometry as assessment of the computational protocol, which has then be used to evinced the importance of the outer coordination shell nature through organic ligand modelization. Magneto-structural correlations as function of internal degrees of freedom for isotropic and anisotropic exchange contributions are also presented, outlining, for the first time, the extremely rapidly changing nature of the anisotropic exchange coupling. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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2964 KiB  
Article
The Trans Influence in Unsymmetrical Pincer Palladacycles: An Experimental and Computational Study
by Sarote Boonseng, Gavin W. Roffe, Rhiannon N. Jones, Graham J. Tizzard, Simon J. Coles, John Spencer and Hazel Cox
Inorganics 2016, 4(3), 25; https://doi.org/10.3390/inorganics4030025 - 11 Aug 2016
Cited by 8 | Viewed by 5480
Abstract
A library of unsymmetrical SCN pincer palladacycles, [ClPd{2-pyr-6-(RSCH2)C6H3}], R = Et, Pr, Ph, p-MePh, and p-MeOPh, pyr = pyridine, has been synthesized via C–H bond activation, and used, along with PCN and N’CN unsymmetrical pincer [...] Read more.
A library of unsymmetrical SCN pincer palladacycles, [ClPd{2-pyr-6-(RSCH2)C6H3}], R = Et, Pr, Ph, p-MePh, and p-MeOPh, pyr = pyridine, has been synthesized via C–H bond activation, and used, along with PCN and N’CN unsymmetrical pincer palladacycles previously synthesized by the authors, to determine the extent to which the trans influence is exhibited in unsymmetrical pincer palladacycles. The trans influence is quantified by analysis of structural changes in the X-ray crystal and density functional theory (DFT) optimized structures and a topological analysis of the electron density using quantum theory of atoms in molecules (QTAIM) to determine the strength of the Pd-donor atom interaction. It is found that the trans influence is controlled by the nature of the donor atom and although the substituents on the donor-ligand affect the Pd-donor atom interaction through the varied electronic and steric constraints, they do not influence the bonding of the ligand trans to it. The data indicate that the strength of the trans influence is P > S > N. Furthermore, the synthetic route to the family of SCN pincer palladacycles presented demonstrates the potential of late stage derivitization for the effective synthesis of ligands towards unsymmetrical pincer palladacycles. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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1358 KiB  
Article
Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)
by Wojciech I. Dzik
Inorganics 2016, 4(3), 21; https://doi.org/10.3390/inorganics4030021 - 05 Jul 2016
Cited by 9 | Viewed by 5208
Abstract
Recently, homogeneous cobalt systems were reported to catalyze the reductive silylation of dinitrogen. In this study the investigations on the silylation of dinitrogen catalyzed by CoH(PPh3)3N2 are presented. We show that in the presence of the title compound, [...] Read more.
Recently, homogeneous cobalt systems were reported to catalyze the reductive silylation of dinitrogen. In this study the investigations on the silylation of dinitrogen catalyzed by CoH(PPh3)3N2 are presented. We show that in the presence of the title compound, the reaction of N2 with trimethylsilylchloride and sodium yields, on average, 6.7 equivalents of tris(trimethylsilyl)amine per Co atom in THF (tetrahydrofuran). The aim was to elucidate whether the active catalyst is: (a) the [Co(PPh3)3N2] anion formed after two-electron reduction of the title compound; or (b) a species formed via decomposition of CoH(PPh3)3N2 in the presence of the highly reactive substrates. Time profile, and IR and EPR spectroscopic investigations show instability of the pre-catalyst under the applied conditions which suggests that the catalytically active species is formed through in situ modification of the pre-catalyst. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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3210 KiB  
Communication
The Viscosity and Intermolecular Interaction of Organic and Inorganic Hybrid Systems Composed of Chiral Schiff Base Ni(II), Cu(II), and Zn(II) Complexes with Long Ligands, Azobenzene, and PMMA
by Hiroshi Takano, Masahiro Takase, Nobumitsu Sunaga, Maiko Ito and Takashiro Akitsu
Inorganics 2016, 4(3), 20; https://doi.org/10.3390/inorganics4030020 - 27 Jun 2016
Cited by 8 | Viewed by 5221
Abstract
We have here synthesized new chiral Schiff base Ni(II), Cu(II), Zn(II) complexes (Ni, Cu, Zn) and hybrid materials with azobenzene (AZ) in polymethyl methacrylate (PMMA). Linearly polarized UV light irradiation of these hybrid materials slightly [...] Read more.
We have here synthesized new chiral Schiff base Ni(II), Cu(II), Zn(II) complexes (Ni, Cu, Zn) and hybrid materials with azobenzene (AZ) in polymethyl methacrylate (PMMA). Linearly polarized UV light irradiation of these hybrid materials slightly increased their optical anisotropy of AZ as well as the complexes, which were measured with polarized IR and UV-Vis spectra and discussed based on TD-DFT calculations. Non-linear concentration (viscosity) dependence of PMMA solutions about artifact peaks suggested weak intermolecular interactions due to the flexibility of complexes by inserted methylene chains. Molecular modeling indicated that large spaces around complexes in PMMA resulted in easy molecular orientation (Ni > Cu > Zn) as short-term saturation of the UV light irradiation. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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790 KiB  
Communication
Monoanionic Tin Oligomers Featuring Sn–Sn or Sn–Pb Bonds: Synthesis and Characterization of a Tris(Triheteroarylstannyl)Stannate and -Plumbate
by Kornelia Zeckert
Inorganics 2016, 4(2), 19; https://doi.org/10.3390/inorganics4020019 - 20 Jun 2016
Cited by 3 | Viewed by 4344
Abstract
The reaction of the lithium tris(2-pyridyl)stannate [LiSn(2-py6OtBu)3] (py6OtBu = C5H3N-6-OtBu), 1, with the element(II) amides E{N(SiMe3)2}2 (E = Sn, Pb) afforded complexes [...] Read more.
The reaction of the lithium tris(2-pyridyl)stannate [LiSn(2-py6OtBu)3] (py6OtBu = C5H3N-6-OtBu), 1, with the element(II) amides E{N(SiMe3)2}2 (E = Sn, Pb) afforded complexes [LiE{Sn(2-py6OtBu)3}3] for E = Sn (2) and E = Pb (3), which reveal three Sn–E bonds each. Compounds 2 and 3 have been characterized by solution NMR spectroscopy and X-ray crystallographic studies. Large 1J(119Sn–119/117Sn) as well as 1J(207Pb–119/117Sn) coupling constants confirm their structural integrity in solution. However, contrary to 2, complex 3 slowly disintegrates in solution to give elemental lead and the hexaheteroarylditin [Sn(2-py6OtBu)3]2 (4). Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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2572 KiB  
Article
Tetrapropylammonium Occlusion in Nanoaggregates of Precursor of Silicalite-1 Zeolite Studied by 1H and 13C NMR
by Mohamed Haouas, David P. Petry, Michael W. Anderson and Francis Taulelle
Inorganics 2016, 4(2), 18; https://doi.org/10.3390/inorganics4020018 - 01 Jun 2016
Cited by 4 | Viewed by 5245
Abstract
The dynamic behavior of tetrapropylammonium (TPA) cations in the clear precursor sols for silicalite synthesis has been investigated by 1H diffusion ordered spectroscopy (DOSY), T1, T2, and T 1H relaxation, as well as 1H→13 [...] Read more.
The dynamic behavior of tetrapropylammonium (TPA) cations in the clear precursor sols for silicalite synthesis has been investigated by 1H diffusion ordered spectroscopy (DOSY), T1, T2, and T 1H relaxation, as well as 1H→13C cross polarization (CP) nuclear magnetic resonance. The DOSY NMR experiments showed the presence of strong solute–solvent interactions in concentrated sols, which are decreasing upon dilution. Similarities in dependence of diffusion coefficients with fractional power of the viscosity constant observed for nanoparticles, TPA cations and water led to the conclusion that they aggregate as anisotropic silicate-TPA particles. Relaxation studies as well as 1H→13C CP experiments provide information on dynamic properties of ethanol, water and TPA cations, which are function of silicate aggregates. The general tendency showed that the presence of silicate as oligomers and particles decreases the relaxation times, in particular T2 and T1ρH, as a consequence of involvement of these latter in ion-pairing interactions with water-solvated TPA molecules slowing down their mobility. Furthermore, from the 1H→13C CP dynamics curve profiles a change in the CP transfer regime was observed from fast (TCH << T1ρH) for solutions without silicates to moderate (TCH~T1ρH) when silicates are interacting with the TPA cations that may reflect the occlusion of TPA into flexible silicate hydrate aggregates. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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2348 KiB  
Article
β,β-Isomer of Open-Wells–Dawson Polyoxometalate Containing a Tetra-Iron(III) Hydroxide Cluster: [{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]9−
by Satoshi Matsunaga, Eriko Miyamae, Yusuke Inoue and Kenji Nomiya
Inorganics 2016, 4(2), 15; https://doi.org/10.3390/inorganics4020015 - 17 May 2016
Cited by 294 | Viewed by 5220
Abstract
The β,β-isomer of open-Wells–Dawson polyoxometalate (POM) containing a tetra-iron(III) cluster, K9[{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]·17H2O (potassium salt of β,β-Fe4-open), was synthesized by reacting Na9H[A-β-SiW9O34 [...] Read more.
The β,β-isomer of open-Wells–Dawson polyoxometalate (POM) containing a tetra-iron(III) cluster, K9[{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]·17H2O (potassium salt of β,β-Fe4-open), was synthesized by reacting Na9H[A-β-SiW9O34]·23H2O with FeCl3·6H2O at pH 3, and characterized by X-ray crystallography, FTIR, elemental analysis, TG/DTA, UV–Vis, and cyclic voltammetry. X-ray crystallography revealed that the {Fe3+4(H2O)(OH)5}7+ cluster was included in the open pocket of the β,β-type open-Wells–Dawson polyanion [β,β-Si2W18O66]16− formed by the fusion of two trilacunary β-Keggin POMs, [A-β-SiW9O34]10−, via two W–O–W bonds. The β,β-open-Wells–Dawson polyanion corresponds to an open structure of the standard γ-Wells–Dawson POM. β,β-Fe4-open is the first example of the compound containing a geometrical isomer of α,α-open-Wells–Dawson structural POM. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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2154 KiB  
Article
Hexacoordinate Silicon Compounds with a Dianionic Tetradentate (N,N′,N′,N)-Chelating Ligand
by Daniela Gerlach, Erica Brendler and Jörg Wagler
Inorganics 2016, 4(2), 8; https://doi.org/10.3390/inorganics4020008 - 14 Apr 2016
Cited by 5 | Viewed by 8237
Abstract
In the context of our systematic investigations of penta- and hexacoordinate silicon compounds, which included dianionic tri- (O,N,O′; O,N,N′) and tetradentate (O,N,N,O; O, [...] Read more.
In the context of our systematic investigations of penta- and hexacoordinate silicon compounds, which included dianionic tri- (O,N,O′; O,N,N′) and tetradentate (O,N,N,O; O,N,N′,O′) chelators, we have now explored silicon coordination chemistry with a dianionic tetradentate (N,N′,N′,N) chelator. The ligand [o-phenylene-bis(pyrrole-2-carbaldimine), H2L] was obtained by condensation of o-phenylenediamine and pyrrole-2-carbaldehyde and subsequently silylated with chlorotrimethylsilane/triethylamine. Transsilylation of this ligand precursor (Me3Si)2L with chlorosilanes SiCl4, PhSiCl3, Ph2SiCl2, (Anis)2SiCl2 and (4-Me2N-C6H4)PhSiCl2 afforded the hexacoordinate Si complexes LSiCl2, LSiPhCl, LSiPh2, LSi(Anis)2 and LSiPh(4-Me2N-C6H4), respectively (Anis = anisyl = 4-methoxyphenyl). 29Si NMR spectroscopy and, for LSiPh2, LSi(Anis)2 and LSiPh(4-Me2N-C6H4), single-crystal X-ray diffraction confirm hexacoordination of the Si atoms. The molecular structures of LSiCl2 and LSiPhCl were elucidated by computational methods. Despite the two different N donor sites (pyrrole N, X-type donor; imine N, L-type donor), charge delocalization within the ligand backbone results in compounds with four similar Si–N bonds. Charge distribution within the whole molecules was analyzed by calculating the Natural Charges (NCs). Although these five compounds carry electronically different monodentate substituents, their constituents reveal rather narrow ranges of their charges (Si atoms: +2.10–+2.22; monodentate substituents: −0.54–−0.56; L2−: −1.02–−1.11). Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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Review

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1452 KiB  
Review
Anion Ordering in Bichalcogenides
by Martin Valldor
Inorganics 2016, 4(3), 23; https://doi.org/10.3390/inorganics4030023 - 22 Jul 2016
Cited by 12 | Viewed by 5789
Abstract
This review contains recent developments and new insights in the research on inorganic, crystalline compounds with two different chalcogenide ions (bichalcogenides). Anion ordering is used as a parameter to form structural dimensionalities as well as local- and global-electric polarities. The reason for the [...] Read more.
This review contains recent developments and new insights in the research on inorganic, crystalline compounds with two different chalcogenide ions (bichalcogenides). Anion ordering is used as a parameter to form structural dimensionalities as well as local- and global-electric polarities. The reason for the electric polarity is that, in the heterogeneous bichalcogenide lattice, the individual bond-lengths between cations and anions are different from those in a homogeneous anion lattice. It is also shown that heteroleptic tetrahedral and octahedral coordinations offer a multitude of new crystal fields and coordinations for involved cations. This coordination diversity in bichalcogenides seems to be one way to surpass electro-chemical redox potentials: three oxidation states of a single transition metal can be stabilized, e.g., Ba15V12S34O3. A new type of disproportionation, related to coordination, is presented and results from chemical pressure on the bichalcogenide lattices of (La,Ce)CrS2O, transforming doubly [CrS3/3S2/2O1/1]3− (5+1) into singly [CrS4/2S2/3]7/3− (6+0) and [CrS4/3O2/1]11/3− (4+2) coordinations. Also, magnetic anisotropy is imposed by the anion ordering in BaCoSO, where magnetic interactions via S or O occur along two different crystallographic directions. Further, the potential of the anion lattice is discussed as a parameter for future materials design. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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3017 KiB  
Review
Advances in Engineered Hemoproteins that Promote Biocatalysis
by Kari L. Stone and Syeda M. Ahmed
Inorganics 2016, 4(2), 12; https://doi.org/10.3390/inorganics4020012 - 04 May 2016
Cited by 4 | Viewed by 5783
Abstract
Some hemoproteins have the structural robustness to withstand extraction of the heme cofactor and replacement with a heme analog. Recent reports have reignited interest and exploration in this field by demonstrating the versatility of these systems. Heme binding proteins can be utilized as [...] Read more.
Some hemoproteins have the structural robustness to withstand extraction of the heme cofactor and replacement with a heme analog. Recent reports have reignited interest and exploration in this field by demonstrating the versatility of these systems. Heme binding proteins can be utilized as protein scaffolds to support heme analogs that can facilitate new reactivity by noncovalent bonding at the heme-binding site utilizing the proximal ligand for support. These substituted hemoproteins have the capability to enhance catalytic reactivity and functionality comparatively to their native forms. This review will focus on progress and recent advances of artificially engineered hemoproteins utilized as a new target for the development of biocatalysts. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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1230 KiB  
Review
Manganese and Iron Catalysts in Alkyd Paints and Coatings
by Ronald Hage, Johannes W. De Boer and Karin Maaijen
Inorganics 2016, 4(2), 11; https://doi.org/10.3390/inorganics4020011 - 29 Apr 2016
Cited by 20 | Viewed by 9805
Abstract
Many paint, ink and coating formulations contain alkyd-based resins which cure via autoxidation mechanisms. Whilst cobalt-soaps have been used for many decades, there is a continuing and accelerating desire by paint companies to develop alternatives for the cobalt soaps, due to likely classification [...] Read more.
Many paint, ink and coating formulations contain alkyd-based resins which cure via autoxidation mechanisms. Whilst cobalt-soaps have been used for many decades, there is a continuing and accelerating desire by paint companies to develop alternatives for the cobalt soaps, due to likely classification as carcinogens under the REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) legislation. Alternative driers, for example manganese and iron soaps, have been applied for this purpose. However, relatively poor curing capabilities make it necessary to increase the level of metal salts to such a level that often coloring of the paint formulation occurs. More recent developments include the application of manganese and iron complexes with a variety of organic ligands. This review will discuss the chemistry of alkyd resin curing, the applications and reactions of cobalt-soaps as curing agents, and, subsequently, the paint drying aspects and mechanisms of (model) alkyd curing using manganese and iron catalysts. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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