Inorganic Chemistry (Inorg Chem )

Publisher: American Chemical Society, American Chemical Society


Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and some aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds. Inorganic Chemistry offers full-length studies, shorter notes, and communications of immediate interest and has earned respect throughout the world for attracting and publishing outstanding research.

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    Inorganic chemistry (Online), Inorganic chemistry
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American Chemical Society

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    • Reviewed on 07/08/2014
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Publications in this journal

  • [Show abstract] [Hide abstract]
    ABSTRACT: Parkinson’s disease (PD) is a neurodegenerative disorder characterized by the presence of abnormal α-synuclein (αS) deposits in the brain. Alterations in homeostasis and metal-induced oxidative stress may play a crucial role in the progression of αS amyloid assembly and pathogenesis of PD. Contrary to αS, β-synuclein (βS) is not involved in the PD etiology. However, it has been suggested that the βS/αS ratio is altered in PD, indicating that a correct balance of these two proteins is implicated in the inhibition of αS aggregation. αS and βS share similar abilities to coordinate Cu(II). In this study, we investigated and compared the interaction of Cu(I) with the N-terminal portion of βS and αS by means of NMR, circular dichroism, and X-ray absorption spectroscopies. Our data show the importance of M10K mutation, which induces different Cu(I) chemical environments. Coordination modes 3S1O and 2S2O were identified for βS and αS, respectively. These new insights into the bioinorganic chemistry of copper and synuclein proteins are a basis to understand the molecular mechanism by which βS might inhibit αS aggregation.
    Inorganic Chemistry 12/2014;
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    ABSTRACT: Electronic structures and magnetic properties of the U4+ complexes (C5Me4H)3UNO, (C5Me4H)3UCl, (C5H5)3UCH3, and (C5H5)3UCl are investigated by quantum chemical calculations. On the basis of wave function calculations including spin−orbit (SO) interactions, all complexes have nondegenerate nonmagnetic ground states. However, for L = CH3 and Cl magnetic doublet excited states are very low in energy, rendering the magnetic susceptibility strongly temperature dependent above ca. 50−100 K. In contrast, (C5Me4H)3UNO exhibits temperature-independent paramagnetism even at room temperature. The calculated susceptibilities agree well with available experimental data. An analysis of the ground states and the magnetic behavior is performed using crystal-field (CF) models with parameters extracted from the ab initio calculations, and with the help of natural orbitals contributing to the electron density, generated from scalar relativistic and SO wave functions for the ground states and selected excited states. Electronic g-factors calculated from the CF models agree well with ab initio data. The U−NO bond order in (C5Me4H)3UNO decreases somewhat due to SO coupling, because U−NO bonding π orbitals with strong U 5fπ character mix with nonbonding 5fδ orbitals under the SO interaction. This complex also exhibits pronounced multireference character. All complexes afford U-ligand 5f covalent character.
    Inorganic Chemistry 11/2014;
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    ABSTRACT: BaMn9[VO4]6(OH)2 was synthesized by hydrothermal methods. We evaluated the crystal structure based on the two possible space groups P213 and Pa3̅ [a = 12.8417(2) Å] using single-crystal and powder X-ray diffraction techniques. The structure contains three-dimensionally linked Mn9 units of a chiral "paddle-wheel" type. Experimental IR and Raman spectra were analyzed in terms of fundamental vanadate and hydroxide vibrational modes. The magnetic properties were investigated, and the specific heat in applied fields was studied. The dominant magnetic interactions (Mn(2+), S = (5)/2) are of antiferromagnetic origin, as indicated by a Curie-Weiss fit above 175 K with Θ ≈ -200 K. Canting of the spins on the geometrically frustrated triangle segment of the structural feature is considered to account for the ferrimagnetic type of long-range order at TC ≈ 18 K. We propose a model for the spin structure in the ordered regime. Dielectric constants were measured and indicate a magnetodielectric effect at TC, which is assigned to spin-lattice coupling.
    Inorganic Chemistry 11/2014;
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    ABSTRACT: Reaction of small increments of NO2 gas with sublimed amorphous layers of Mn(II)(TPP) (TPP = meso-tetra-phenylporphyrinato dianion) in a vacuum cryostat leads to formation of the 5-coordinate monodentate nitrato complex Mn(III)(TPP)(η(1)-ONO2) (II). This transformation proceeds through the two distinct steps with initial formation of the five coordinate O-nitrito complex Mn(III)(TPP)(η(1)-ONO) (I) as demonstrated by the electronic absorption spectra and by FTIR spectra using differently labeled nitrogen dioxide. A plausible mechanism for the second stage of reaction is offered based on the spectral changes observed upon subsequent interaction of (15)NO2 and NO2 with the layered Mn(TPP). Low-temperature interaction of I and II with the vapors of various ligands L (L = O-, S-, and N-donors) leads to formation of the 6-coordinate O-nitrito Mn(III)(TPP)(L)(η(1)-ONO) and monodentate nitrato Mn(III)(TPP)(L)(η(1)-ONO2) complexes, respectively. Formation of the 6-coordinate O-nitrito complex is accompanied by the shifts of the ν(N═O) band to lower frequency and of the ν(N-O) band to higher frequency. The frequency difference between these bands Δν = ν(N═O) - ν(N-O) is a function of L and is smaller for the stronger bases. Reaction of excess NH3 with I leads to formation of Mn(TPP)(NH3)(η(1)-ONO) and of the cation [Mn(TPP)(NH3)2](+) plus ionic nitrite. The nitrito complexes are relatively unstable, but several of the nitrato species can be observed in the solid state at room temperature. For example, the tetrahydrofuran complex Mn(TPP)(THF)(η(1)-ONO2) is stable in the presence of THF vapors (∼5 mm), but it loses this ligand upon high vacuum pumping at RT. When L = dimethylsulfide (DMS), the nitrato complex is stable only to ∼-30 °C. Reactions of II with the N-donor ligands NH3, pyridine, or 1-methylimidazole are more complex. With these ligands, the nitrato complexes Mn(III)(TPP)(L)(η(1)-ONO2) and the cationic complexes [Mn(TPP)(L)2](+) coexist in the layer at room temperature, the latter formed as a result of NO3(-) displacement when L is in excess.
    Inorganic Chemistry 11/2014; 53((22)):11948–11959.
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    ABSTRACT: The heptadentate ligand OBETA (2,2'-oxybis(ethylamine)-N,N,N',N'-tetraacetic acid) was reported to form complexes with Ln(3+) ions more stable than those formed by the octadentate and more popular congener EGTA (ethylene glycol O,O'-bis(ethylamine)-N,N,N',N'-tetraacetic acid). The structural features leading to this puzzling coordination paradox were investigated by X-ray diffraction, solution state NMR, molecular modeling, and relaxometric studies. The stability constant of Gd(OBETA) (log KGdL = 19.37, 0.1 M KCl) is 2 orders of magnitude higher than that of the higher denticity analogue Gd(EGTA) (log KGdL = 17.66, 0.1 M KCl). The half-lives (t1/2) for the dissociation reactions of Gd(OBETA) and Gd(EGTA) ([Cu(2+)]tot = 0.2 mM, [Cit(3-)]tot = 0.5 mM, [PO4(3-)]tot = 1.0 mM, and [CO3(2-)]tot = 25 mM at pH = 7.4 and 25 °C in 0.1 M KCl solution) are 6.8 and 0.63 h, respectively, reflecting the much higher inertness of Gd(OBETA) near physiological conditions. NMR studies and DFT calculations using the B3LYP functional and a large-core ECP indicate that the [Gd(OBETA)(H2O)2](-) complex most likely exists in solution as the Δ(λλ)(δδδδ)A/Λ(δδ)(λλλλ)A enantiomeric pair, with an activation free energy for the enantiomerization process of ∼40 kJ·mol(-1). The metal ion is nine-coordinate by seven donor atoms of the ligand and two inner-sphere water molecules. The X-ray crystal structure of [C(NH2)3]3[Lu(OBETA)(CO3)]·2H2O is in agreement with the predictions of DFT calculations, the two coordinated water molecules being replaced by a bidentate carbonate anion. The (1)H NMRD and (17)O NMR study revealed that the two inner-sphere water molecules in Gd(OBETA) are endowed with a relatively fast water exchange rate (kex(298) = 13 × 10(6) s(-1)). The higher thermodynamic stability and inertness of Ln(OBETA) complexes, peaking in the center of the 4f series, combined with the presence of two coordinated water molecules suggests that Gd(OBETA) is a promising paramagnetic probe for MRI applications.
    Inorganic Chemistry 11/2014;
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    ABSTRACT: The synthesis, crystal structure, magnetic properties, and europium Mössbauer spectroscopy of the new members of the 9-4-9 Zintl family of Eu9Cd4-xCM2+x-y□ySb9 (CM = coinage metal: Au, Ag, and Cu) are reported. These compounds crystallize in the Ca9Mn4Bi9 structure type (9-4-9) with the 4g interstitial site almost half-occupied by coinage metals; these are the first members in the 9-4-9 family where the interstitial positions are occupied by a monovalent metal. All previously known compounds with this structure type include divalent interstitials where these interstitials are typically the same as the transition metals in the anionic framework. Single-crystal magnetic susceptibility data indicate paramagnetic behavior for all three compounds with antiferromagnetic ordering below 10 K (at 100 Oe) that shifts to lower temperature (<7 K) by applying a 3 T magnetic field. (151)Eu Mössbauer spectra were collected on polycrystalline powder samples of Eu9Cd4-xCM2+x-y□ySb9 at 50 and 6.5 K in order to evaluate the valence of Eu cations. Although the Zintl formalism states that the five crystallographically distinct Eu sites in Eu9Cd4-xCM2+x-y□ySb9 should bear Eu(2+), the Mössbauer spectral isomer shifts are clearly indicative of both 2+ and 3+ valence of the Eu cations with the Cu- and Au-containing compounds showing higher amounts of Eu(3+). This electronic configuration leads to an excess of negative charge in these compounds that contradicts the expected valence-precise requirement of Zintl phases. The spectra obtained at 6.5 K reveal magnetic ordering for both Eu(2+) and Eu(3+). The field dependence of Eu(2+) indicates two distinct magnetic sublattices, with higher and lower fields, and of a small field for Eu(3+). The site symmetry of the five Eu sites is not distinguishable from the Mössbauer data.
    Inorganic Chemistry 10/2014;
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    ABSTRACT: The first four uranyl peroxide compounds containing ethylenediaminetetra-acetate (EDTA) were synthesized and characterized from aqueous uranyl peroxide nitrate solutions with a pH range of 5-7. Raman spectra demonstrated that reaction solutions that crystallized [NaK15[(UO2)8(O2)8(C10H12O10N2)2(C2O4)4]·(H2O)14] (1) and [Li4K6[(UO2)8(O2)6(C10H12O10N2)2(NO3)6]·(H2O)26] (2) contained excess peroxide, and their structures contained oxidized ethylenediaminetetraacetate, EDTAO2(4-). The solutions from which [K4[(UO2)4(O2)2(C10H13O8N2)2(IO3)2]·(H2O)16] (3) and LiK3[(UO2)4(O2)2(C10H12O8N2)2(H2O)2]·(H2O)18 (4) crystallized contained no free peroxide, and the structures incorporated intact EDTA(4-). In contrast to the large family of uranyl peroxide cage clusters, coordination of uranyl peroxide units in 1-4 by EDTA(4-) or EDTAO2(4-) results in isolated tetramers or dimers of uranyl ions that are bridged by bidentate peroxide groups. Two tetramers are bridged by EDTAO2(4-) to form octamers in 1 and 2, and dimers of uranyl polyhedra are linked through iodate groups in 3 and EDTA(4-) in 4, forming chains in both cases. In each structure the U-O2-U dihedral angle is strongly bent, at ∼140°, consistent with the configuration of this linkage in cage clusters and other recently reported uranyl peroxides.
    Inorganic Chemistry 10/2014;
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    ABSTRACT: The polycrystalline, high-pressure PdF2 forms of MO2 (HP-PdF2-type MO2, M = Rh, Os, Pt) compounds were successfully synthesized under high-pressure conditions for the first time, to the best of our knowledge. The crystal structures and electromagnetic properties were studied. Previously unreported electronic properties of the polycrystalline HPPdF2-type RuO2 and IrO2 were also studied. The refined structures clearly indicated that all compounds crystallized into the HP-PdF2-type structure, M4+O2−2, rather than the pyritetype structure, Mn+(O2)n− (n < 4). The MO2 compounds (M = Ru, Rh, Os, Ir) exhibited metallic conduction, while PtO2 was highly insulating, probably because of the fully occupied t2g band. Neither superconductivity nor a magnetic transition was detected down to a temperature of 2 K, unlike the case of 3d transition metal chalcogenide pyrites.
    Inorganic Chemistry 10/2014;
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    ABSTRACT: A one-electron reduction of osmium(IV) complexes trans-[Os(IV)Cl4(Hazole)2], where Hazole = 1H-pyrazole ([1](0)), 2H-indazole ([2](0)), 1H-imidazole ([3](0)), and 1H-benzimidazole ([4](0)), afforded a series of eight new complexes as osmium analogues of KP1019, a lead anticancer drug in clinical trials, with the general formula (cation)[trans-Os(III)Cl4(Hazole)2], where cation = H2pz(+) (H2pz[1]), H2ind(+) (H2ind[2]), H2im(+) (H2im[3]), Ph4P(+) (Ph4P[3]), nBu4N(+) (nBu4N[3]), H2bzim(+) (H2bzim[4]), Ph4P(+) (Ph4P[4]), and nBu4N(+) (nBu4N[4]). All complexes were characterized by elemental analysis, (1)H NMR spectroscopy, electrospray ionization mass spectrometry, UV-vis spectroscopy, cyclic voltammetry, while H2pz[1], H2ind[2], and nBu4[3], in addition, by X-ray diffraction. The reduced species [1](-) and [4](-) are stable in aqueous media in the absence of air oxygen and do not react with small biomolecules such as amino acids and the nucleotide 5'-dGMP. Cell culture experiments in five different human cancer cell lines (HeLa, A549, FemX, MDA-MB-453, and LS-174) and one noncancerous cell line (MRC-5) were performed, and the results were discussed and compared to those for KP1019 and cisplatin. Benzannulation in complexes with similar structure enhances antitumor activity by several orders of magnitude, implicating different mechanisms of action of the tested compounds. In particular, complexes H2ind[2] and H2bzim[4] exhibited significant antiproliferative activity in vitro when compared to H2pz[1] and H2im[3].
    Inorganic Chemistry 10/2014;
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    ABSTRACT: A new alkaline thorium arsenate family was obtained and systematically investigated. The structures of A2Th(AsO4)2 (A = Li, Na, K, Rb, Cs) were determined from single crystal X-ray diffraction data. Li2Th(AsO4)2 and either isostructural K2Th(AsO4)2 and Rb2Th(AsO4)2 crystallize in the monoclinic crystal system. Na2Th(AsO4)2 and Cs2Th(AsO4)2 crystallize in the orthorhombic and tetragonal crystal systems, respectively. Li2Th(AsO4)2 consists of [Th(AsO4)2](2-) layers with Li atoms in the interlayer space. The rest of the compounds are based on 3D frameworks. Differences in local environments of ThO8 coordination polyhedra are described in relation to the symmetry. Despite different local environments of ThO8 coordination polyhedra and different structural symmetry, underlying nets of A2Th(AsO4)2 (A = Na, K, Rb, Cs) were shown to be the same. Single-crystal and powder Raman spectra were measured, and bands are assigned. DSC measurements showed phase transitions in K2Th(AsO4)2 and Rb2Th(AsO4)2, which were studied using high-temperature powder X-ray diffraction (HT-PXRD). The data of HT-PXRD demonstrates two high-temperature polymorphic modification of K2Th(AsO4)2 and only one for the isotypic Rb2Th(AsO4)2. The phase transitions in both K and Rb phases are reversible.
    Inorganic Chemistry 10/2014;
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    ABSTRACT: Probing the local environment of low-Z elements such as oxygen is of great interest for understanding the atomic scale behavior in materials, but it requires experimental techniques allowing to work with versatile sample environments. In this paper, the local environment of lithium borate crystals is investigated using non-resonant inelastic X-ray scattering (NRIXS) at energy losses corresponding to the oxygen K-edge. Large variations of the spectral features are observed close to the edge onset, in the 535-540 eV energy range when varying the Li2O content. Theoretical calculations allow identification of contributions associated with bridging oxygen (BO) and non-bridging oxygen (NBO) atoms. The main result resides in the observed core level shift of about 1.7 eV separa-tion in the spectral signatures of the BO and the NBO. The clear signature at 535 eV in the O K-edge NRXIS spectrum is then an original way to probe the presence of NBOs in borates, with the great advantage of making possible the use of complex environments such as high-pressure cell or high-temperature device for in situ measurements.
    Inorganic Chemistry 10/2014;
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    ABSTRACT: Three dinucleating Ru-Cl complexes containing the hexadentate dinucleating ligand [1,1'-(4-methyl-1H-pyrazole-3,5-diyl)bis(1-(pyridin-2-yl)ethanol)] (Hpbl) and the meridional 2,2':6',2″-terpyridine ligand (trpy) have been prepared and isolated. These complexes include {[RuCl(trpy)]2(μ-pbl-κ-N(3)O)}(+) (1a(+)), {[RuCl(trpy)]2(μ-Hpbl-κ-N(3)O)}(2+) (1b(2+)), and {[RuCl(trpy)]2(μ-Hpbl-κ-N(2)O(2))}(2+) (1c(2+)) and were characterized by analytic and spectroscopic techniques. In addition, complexes 1b(2+) and 1c(2+) were characterized in the solid state by monocrystal X-ray diffraction analysis. The coordination versatility of the Hpbl ligand allows the presence of multiple isomers that can be obtained depending on the Ru oxidation state and were thoroughly characterized by electrochemical techniques, namely, cyclic voltammetry and coulometry. Finally, 1a(+) and its recently reported mononuclear analogue, in-[RuCl(Hpbl)(trpy)](+), have been tested as catalysts for epoxidation of cis-β-methylstyrene.
    Inorganic Chemistry 09/2014;
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    ABSTRACT: We have recently reported a deprotonation-induced valence inversion within a phenoxido-bridged mixed-valent diiron(II,III) complex. The initial aniline coordinated to the FeII site reacts with triethylamine, and the resulting complex contains an anilide ligand coordinated to the FeIII ion. The behavior of these complexes in acetonitrile is indeed more intricate. Owing to the very distinctive spectroscopic signatures of the complexes, the conjunction of NMR, Mössbauer, and UV–visible absorption spectroscopies allows one to evidence two isomerization reactions, one involving the aniline linked to FeII and the other the anilide on FeIII. Theoretical calculations sustain this conclusion. Aniline in the cis position versus the bridging phenoxide is shown to be the most stable isomer while the anilide trans to the phenoxido bridge is favored. The trans isomer of the aniline complex is more acidic than the cis one by 1 pKa unit. Isomerization of the anilide complex is 10 times faster than the analogous isomerization of the aniline complex. Both reactions are proposed to proceed through a unique mechanism. This is the first time that such isomerization reactions are evidenced in dinuclear complexes.
    Inorganic Chemistry 09/2014;