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Inorganics, Volume 7, Issue 4 (April 2019)

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Cover Story (view full-size image) The cover shows sections of the X-ray diffraction pattern and the crystal structure of the [...] Read more.
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Open AccessReview
The S3 State of the Oxygen-Evolving Complex: Overview of Spectroscopy and XFEL Crystallography with a Critical Evaluation of Early-Onset Models for O–O Bond Formation
Received: 7 March 2019 / Revised: 5 April 2019 / Accepted: 14 April 2019 / Published: 22 April 2019
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Abstract
The catalytic cycle of the oxygen-evolving complex (OEC) of photosystem II (PSII) comprises five intermediate states Si (i = 0–4), from the most reduced S0 state to the most oxidized S4, which spontaneously evolves dioxygen. The precise geometric [...] Read more.
The catalytic cycle of the oxygen-evolving complex (OEC) of photosystem II (PSII) comprises five intermediate states Si (i = 0–4), from the most reduced S0 state to the most oxidized S4, which spontaneously evolves dioxygen. The precise geometric and electronic structure of the Si states, and hence the mechanism of O–O bond formation in the OEC, remain under investigation, particularly for the final steps of the catalytic cycle. Recent advances in protein crystallography based on X-ray free-electron lasers (XFELs) have produced new structural models for the S3 state, which indicate that two of the oxygen atoms of the inorganic Mn4CaO6 core of the OEC are in very close proximity. This has been interpreted as possible evidence for “early-onset” O–O bond formation in the S3 state, as opposed to the more widely accepted view that the O–O bond is formed in the final state of the cycle, S4. Peroxo or superoxo formation in S3 has received partial support from computational studies. Here, a brief overview is provided of spectroscopic information, recent crystallographic results, and computational models for the S3 state. Emphasis is placed on computational S3 models that involve O–O formation, which are discussed with respect to their agreement with structural information, experimental evidence from various spectroscopic studies, and substrate exchange kinetics. Despite seemingly better agreement with some of the available crystallographic interpretations for the S3 state, models that implicate early-onset O–O bond formation are hard to reconcile with the complete line of experimental evidence, especially with X-ray absorption, X-ray emission, and magnetic resonance spectroscopic observations. Specifically with respect to quantum chemical studies, the inconclusive energetics for the possible isoforms of S3 is an acute problem that is probably beyond the capabilities of standard density functional theory. Full article
(This article belongs to the Special Issue Recent Advances in Water Oxidation Catalysis)
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Open AccessReview
Laser Ablation Inductively Coupled Plasma Spectrometry: Metal Imaging in Experimental and Clinical Wilson Disease
Received: 12 March 2019 / Revised: 14 April 2019 / Accepted: 17 April 2019 / Published: 19 April 2019
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Abstract
Wilson disease is an inherited disorder caused by mutations in the ATP7B gene resulting in copper metabolism disturbances. As a consequence, copper accumulates in different organs with most common presentation in liver and brain. Chelating agents that nonspecifically chelate copper, and promote its [...] Read more.
Wilson disease is an inherited disorder caused by mutations in the ATP7B gene resulting in copper metabolism disturbances. As a consequence, copper accumulates in different organs with most common presentation in liver and brain. Chelating agents that nonspecifically chelate copper, and promote its urinary excretion, or zinc salts interfering with the absorption of copper from the gastrointestinal tract, are current medications. Also gene therapy, restoring ATP7B gene function or trials with bis-choline tetrathiomolybdate (WTX101) removing excess copper from intracellular hepatic copper stores and increasing biliary copper excretion, is promising in reducing body’s copper content. Therapy efficacy is mostly evaluated by testing for evidence of liver disease and neurological symptoms, hepatic synthetic functions, indices of copper metabolisms, urinary copper excretions, or direct copper measurements. However, several studies conducted in patients or Wilson disease models have shown that not only the absolute concentration of copper, but also its spatial distribution within the diseased tissue is relevant for disease severity and outcome. Here we discuss laser ablation inductively coupled plasma spectrometry imaging as a novel method for accurate determination of trace element concentrations with high diagnostic sensitivity, spatial resolution, specificity, and quantification ability in experimental and clinical Wilson disease specimens. Full article
(This article belongs to the Special Issue Metals in Neurodegenerative Diseases)
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Open AccessArticle
Pyridine-2,6-Dicarboxylic Acid Esters (pydicR2) as O,N,O-Pincer Ligands in CuII Complexes
Received: 15 February 2019 / Revised: 31 March 2019 / Accepted: 9 April 2019 / Published: 14 April 2019
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Abstract
The pyridine-2,6-carboxylic esters pydicR2 with R = Me or Ph form the unprecedented mononuclear CuII complexes [Cu(pydicR2)Cl3] in one-pot reactions starting from pyridine-2,6-carboxychloride pydicCl2, CuII chloride, and NEt3 in MeOH or PhOH [...] Read more.
The pyridine-2,6-carboxylic esters pydicR2 with R = Me or Ph form the unprecedented mononuclear CuII complexes [Cu(pydicR2)Cl3] in one-pot reactions starting from pyridine-2,6-carboxychloride pydicCl2, CuII chloride, and NEt3 in MeOH or PhOH solution under non-aqueous conditions. The triethylammonium salts (HNEt3)[Cu(pydicR2)Cl3] were isolated. The methyl derivative could be crystallized to allow a XRD structure determination. Both structures were optimized using DFT calculations in various surroundings ranging from gas phase and the non-coordinating solvent CH2Cl2 to the weakly coordinating acetone and well-coordinating solvents acetonitrile (MeCN) or dimethylformamide (DMF), while detailed calculation showed the charge distribution, dipole moments, and HOMO–LUMO gap energies changing upon solvation. According to these calculations, the ion pairs and the anionic CuII complexes were stable, which shows only Cu–Cl bond elongation and weakening of the charge transfer between the anionic complex and the cation as solvents become polar. Synthesis attempts in the presence of water yielded the CuII complexes [Cu(pydic)(OH2)2]n and [Cu(OH2)6][{Cu(pydic)}2(µ-Cl)2], which results from pydicCl2 hydrolysis. Alternatively, the new pydic(IPh)2 (IPh = 2-iodo-phenyl) ester ligand was synthesized and reacted with anhydrous CuCl2, which yields the new binuclear complex [{Cu(pydic(IPh)2)Cl}2(µ-Cl)2]. EPR spectroscopy of the solid compounds reveals typical axial spectra in line with the observed and DFT calculated geometries. Cyclic voltammetry and UV–vis absorption spectroscopy in solution are in line with un-dissociated complex species [Cu(pydicR2)Cl3]. Full article
(This article belongs to the Special Issue First-Row Transition Metal Complexes)
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Open AccessArticle
Electronic Structure of Cubane-Like Vanadium–Nitrogen Cationic Clusters [V4N4]+ and [V6N6]+
Received: 20 March 2019 / Revised: 2 April 2019 / Accepted: 4 April 2019 / Published: 12 April 2019
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Abstract
Density Functional Theory and Complete Active Space Self-Consistent Field (CASSCF) methodologies are used to explore the electronic structure of the cationic V–N clusters, [V4N4]+ and [V6N6]+, that have been identified in recent [...] Read more.
Density Functional Theory and Complete Active Space Self-Consistent Field (CASSCF) methodologies are used to explore the electronic structure of the cationic V–N clusters, [V4N4]+ and [V6N6]+, that have been identified in recent mass spectrometric experiments. Our calculations indicate that both clusters are based on cubane-like fragments of the rock-salt lattice. In the smaller [V4N4]+ cluster, the V–V bonding is delocalized over the tetrahedron, with net bond orders of 1/3 per V–V bond. In [V6N6]+, in contrast, the V–V bonding is strongly localized in the central V2N2 unit, which has a short V=V double bond. CASSCF calculations reveal that both localized and delocalized V–V bonds are highly multi-configurational. Full article
(This article belongs to the Special Issue Applications of Density Functional Theory in Inorganic Chemistry)
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Open AccessArticle
The Lowest-Energy Isomer of C2Si2H4 Is a Bridged Ring: Reinterpretation of the Spectroscopic Data Based on DFT and Coupled-Cluster Calculations
Received: 28 February 2019 / Revised: 2 April 2019 / Accepted: 3 April 2019 / Published: 11 April 2019
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Abstract
The lowest-energy isomer of C2Si2H4 is determined by high-accuracy ab initio calculations to be the bridged four-membered ring 1,2-didehydro-1,3-disilabicyclo[1.1.0]butane (1), contrary to prior theoretical and experimental studies favoring the three-member ring silylsilacyclopropenylidene (2). These [...] Read more.
The lowest-energy isomer of C 2 Si 2 H 4 is determined by high-accuracy ab initio calculations to be the bridged four-membered ring 1,2-didehydro-1,3-disilabicyclo[1.1.0]butane (1), contrary to prior theoretical and experimental studies favoring the three-member ring silylsilacyclopropenylidene (2). These and eight other low-lying minima on the potential energy surface are characterized and ordered by energy using the CCSD(T) method with complete basis set extrapolation, and the resulting benchmark-quality set of relative isomer energies is used to evaluate the performance of several comparatively inexpensive approaches based on many-body perturbation theory and density functional theory (DFT). Double-hybrid DFT methods are found to provide an exceptional balance of accuracy and efficiency for energy-ordering isomers. Free energy profiles are developed to reason the relatively large abundance of isomer 2 observed in previous measurements. Infrared spectra and photolysis reaction mechanisms are modeled for isomers 1 and 2, providing additional insight about previously reported spectra and photoisomerization channels. Full article
(This article belongs to the Special Issue Applications of Density Functional Theory in Inorganic Chemistry)
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Open AccessArticle
Electrochemical and Computational Insights into the Reduction of [Fe2(CO)6{µ-(SCH2)2GeMe2}] Hydrogenase H-Cluster Mimic
Received: 8 February 2019 / Revised: 25 March 2019 / Accepted: 26 March 2019 / Published: 10 April 2019
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Abstract
The electrochemical reduction of the complex [Fe2(CO)6{µ-(SCH2)2GeMe2}] (1) under N2 and CO is reported applying cyclic voltammetry. Reduction of complex 1 in CO saturated solutions prevents the possible [...] Read more.
The electrochemical reduction of the complex [Fe2(CO)6{µ-(SCH2)2GeMe2}] (1) under N2 and CO is reported applying cyclic voltammetry. Reduction of complex 1 in CO saturated solutions prevents the possible release of CO from the dianion 12−, while the latter reacts with additional CO forming a spectroscopically uncharacterized product P1. This product undergoes a reversible redox process at E1/2 = −0.70 V (0.2 V∙s−1). In this report, the structure of the neutral complex 1, isomers of dianionic form of 1, and P1 are described applying DFT computations. Furthermore, we propose reaction pathways for H2 production on the basis of the cyclic voltammetry of complex 1 in presence of the strong acid CF3SO3H. Full article
(This article belongs to the Special Issue Binuclear Complexes)
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Open AccessReview
High-Pressure Routes to New Pyrochlores and Novel Magnetism
Received: 15 February 2019 / Revised: 15 March 2019 / Accepted: 26 March 2019 / Published: 2 April 2019
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Abstract
The pyrochlore structure (A2B2O7) has been an object of consistent study by materials scientists largely due to the stability of the cubic lattice with respect to a wide variety of chemical species on the A or B [...] Read more.
The pyrochlore structure (A2B2O7) has been an object of consistent study by materials scientists largely due to the stability of the cubic lattice with respect to a wide variety of chemical species on the A or B sites. The criterion for stability under ambient conditions is controlled by the ratio of these cations, which is empirically 1.36 < RA/RB < 1.71. However, under applied pressure synthesis conditions, the pyrochlore lattice is stable up to RA/RB ∼ 2.30, opening up possibilities for new compounds. In this review, we will highlight recent work in exploring new rare-earth pyrochlores such as the germanates RE2Ge2O7 and platinates RE2Pt2O7. We highlight recent discoveries made in these pyrochlores such as highly correlated spin ice behavior, spin liquid ground states, and exotic magnetic ordering. Full article
(This article belongs to the Special Issue Magnetic Oxide Materials)
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Open AccessArticle
Stabilization of Supramolecular Networks of Polyiodides with Protonated Small Tetra-azacyclophanes
Received: 1 March 2019 / Revised: 21 March 2019 / Accepted: 26 March 2019 / Published: 1 April 2019
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Abstract
Polyiodide chemistry is among the first historically reported examples of supramolecular forces at work. To date, owing to the increasingly recognized role of halogen bonding and the incorporation of iodine-based components in several devices, it remains an active field of theoretical and applied [...] Read more.
Polyiodide chemistry is among the first historically reported examples of supramolecular forces at work. To date, owing to the increasingly recognized role of halogen bonding and the incorporation of iodine-based components in several devices, it remains an active field of theoretical and applied research. Herein we re-examine azacyclophanes as a class of ligands for the stabilization of iodine-dense three-dimensional networks, showing how we devised novel possible strategies starting from literature material. The new set of azacyclophane ligands affords novel crystal structures possessing intriguing properties, which develop on a double layer. At a macroscopic level, the obtained networks possess a very high iodine packing density (less than 2 times more diluted than crystalline I2): a simple parameter, IN, is also introduced to quickly measure and compare iodine packing density in different crystals. On the microscopic level, the present study provides evidence about the ability of one of the ligands to act as a three-dimensional supramolecular mold for the template synthesis of the rarely observed heptaiodide (I7) anion. Therefore, we believe our approach and strategy might be relevant for crystal engineering purposes. Full article
(This article belongs to the Special Issue Novel Non-Covalent Interactions)
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Open AccessArticle
A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?
Received: 14 February 2019 / Revised: 8 March 2019 / Accepted: 15 March 2019 / Published: 28 March 2019
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Abstract
The intrinsic bonding nature of λ3-iodanes was investigated to determine where its hypervalent bonds fit along the spectrum between halogen bonding and covalent bonding. Density functional theory with an augmented Dunning valence triple zeta basis set (ωB97X-D/aug-cc-pVTZ) coupled with [...] Read more.
The intrinsic bonding nature of λ 3 -iodanes was investigated to determine where its hypervalent bonds fit along the spectrum between halogen bonding and covalent bonding. Density functional theory with an augmented Dunning valence triple zeta basis set ( ω B97X-D/aug-cc-pVTZ) coupled with vibrational spectroscopy was utilized to study a diverse set of 34 hypervalent iodine compounds. This level of theory was rationalized by comparing computational and experimental data for a small set of closely-related and well-studied iodine molecules and by a comparison with CCSD(T)/aug-cc-pVTZ results for a subset of the investigated iodine compounds. Axial bonds in λ 3 -iodanes fit between the three-center four-electron bond, as observed for the trihalide species IF 2 and the covalent FI molecule. The equatorial bonds in λ 3 -iodanes are of a covalent nature. We explored how the equatorial ligand and axial substituents affect the chemical properties of λ 3 -iodanes by analyzing natural bond orbital charges, local vibrational modes, the covalent/electrostatic character, and the three-center four-electron bonding character. In summary, our results show for the first time that there is a smooth transition between halogen bonding → 3c–4e bonding in trihalides → 3c–4e bonding in hypervalent iodine compounds → covalent bonding, opening a manifold of new avenues for the design of hypervalent iodine compounds with specific properties. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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Open AccessArticle
Dimethyloxonium and Methoxy Derivatives of nido-Carborane and Metal Complexes Thereof
Received: 27 February 2019 / Revised: 21 March 2019 / Accepted: 22 March 2019 / Published: 27 March 2019
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Abstract
9-Dimethyloxonium, 10-dimethyloxonium, 9-methoxy and 10-methoxy derivatives of nido-carborane (9-Me2O-7,8-C2B9H11, 10-Me2O-7,8-C2B9H11, [9-MeO-7,8-C2B9H11], and [10-MeO-7,8-C2B9H11 [...] Read more.
9-Dimethyloxonium, 10-dimethyloxonium, 9-methoxy and 10-methoxy derivatives of nido-carborane (9-Me2O-7,8-C2B9H11, 10-Me2O-7,8-C2B9H11, [9-MeO-7,8-C2B9H11], and [10-MeO-7,8-C2B9H11], respectively) were prepared by the reaction of the parent nido-carborane [7,8-C2B9H12] with mercury(II) chloride in a mixture of benzene and dimethoxymethane. Reactions of the 9 and 10-dimethyloxonium derivatives with triethylamine, pyridine, and 3-methyl-6-nitro-1H-indazole result in their N-methylation with the formation of the corresponding salts with 9 and 10-methoxy-nido-carborane anions. The reaction of the symmetrical methoxy derivative [10-MeO-7,8-C2B9H11] with anhydrous FeCl2 in tetrahydrofuran in the presence of t-BuOK results in the corresponding paramagnetic iron bis(dicarbollide) complex [8,8′-(MeO)2-3,3′-Fe(1,2-C2B9H10)2], whereas the similar reactions of the asymmetrical methoxy derivative [9-MeO-7,8-C2B9H11] with FeCl2 and CoCl2 presumably produce the 4,7′-isomers [4,7′-(MeO)2-3,3′-M(1,2-C2B9H10)2] (M = Fe, Co) rather than a mixture of rac-4,7′- and meso-4,4′-isomers. Full article
(This article belongs to the Special Issue Metal Complexes Containing Boron Based Ligands)
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Open AccessArticle
Low-Temperature Ordering in the Cluster Compound (Bi8)Tl[AlCl4]3
Received: 25 February 2019 / Revised: 18 March 2019 / Accepted: 18 March 2019 / Published: 27 March 2019
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Abstract
The reaction of Bi, BiCl3, and TlCl in the ionic liquid [BMIm]Cl·4AlCl3 (BMIm = 1-n-butyl-3-methylimidazolium) at 180 °C yielded air-sensitive black crystals of (Bi8)Tl[AlCl4]3. X-ray diffraction on single crystals at room temperature [...] Read more.
The reaction of Bi, BiCl3, and TlCl in the ionic liquid [BMIm]Cl·4AlCl3 (BMIm = 1-n-butyl-3-methylimidazolium) at 180 °C yielded air-sensitive black crystals of (Bi8)Tl[AlCl4]3. X-ray diffraction on single crystals at room temperature revealed a structure containing [ Tl ( AlCl 4 ) 3 ] 1 2 strands separated by isolated Bi82+ square antiprisms. The thallium(I) ion is coordinated by twelve Cl ions of six [AlCl4] groups, resulting in a chain of face-sharing [TlCl12]11− icosahedra. The Bi82+ polycation is disordered, simulating a threefold axis through its center and overall hexagonal symmetry (space group P63/m). Slowly cooling the crystals to 170 K resulted in increased order in the Bi8 cluster orientations. An ordered structure model in a supercell with a’ = 2a, b’ = 2b, c’ = 3c and the space group P65 was refined. The structure resembles a hexagonal perovskite, with complex groups in place of simple ions. Full article
(This article belongs to the Special Issue Structure, Properties, and Bonding in Solid State Compounds)
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Open AccessArticle
Hexaborate(2−) and Dodecaborate(6−) Anions as Ligands to Zinc(II) Centres: Self-Assembly and Single-Crystal XRD Characterization of [Zn{κ3O-B6O7(OH)6}(κ3N-dien)]·0.5H2O (dien = NH(CH2–CH2NH2)2), (NH4)2[Zn{κ2O-B6O7(OH)6}2 (H2O)2]·2H2O and (1,3-pnH2)3[(κ1N-H3N{CH2}3NH2) Zn{κ3O-B12O18(OH)6}]2·14H2O (1,3-pn = 1,3-diaminopropane)
Received: 27 February 2019 / Revised: 20 March 2019 / Accepted: 23 March 2019 / Published: 27 March 2019
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Abstract
Two zinc(II) hexaborate(2−) complexes, [Zn{κ3O-B6O7(OH)6}(κ3N-dien)]·0.5H2O (dien = NH(CH2CH2NH2)2) (1) and (NH4)2[Zn{κ2O-B6O [...] Read more.
Two zinc(II) hexaborate(2−) complexes, [Zn{κ3O-B6O7(OH)6}(κ3N-dien)]·0.5H2O (dien = NH(CH2CH2NH2)2) (1) and (NH4)2[Zn{κ2O-B6O7(OH)6}2(H2O)2]·2H2O (2), and a zinc(II) dodecaborate(6−) complex, (1,3-pnH2)3[(κ1N-H3N{CH2}3NH2)Zn{κ3O-B12O18(OH)6}]2·14H2O (1,3-pn = 1,3-diaminopropane) (3), have been synthesized and characterized by single-crystal XRD studies. The complexes crystallized through self-assembly processes, from aqueous solutions containing 10:1 ratios of B(OH)3 and appropriate Zn(II) amine complex: [Zn(dien)2](OH)2, [Zn(NH3)4](OH)2, and [Zn(pn)3](OH)2. The hexaborate(2−) anions in 1 and 2 are coordinated to octahedral Zn(II) centres as tridentate (1) or bidentate ligands (2) and the dodecaborate(6−) ligand in 3 is tridentate to a tetrahedral Zn(II) centre. Full article
(This article belongs to the Special Issue Metal Complexes Containing Boron Based Ligands)
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Open AccessArticle
Electronic Effects of the Substituents on Relaxometric and CEST Behaviour of Ln(III)-DOTA-Tetraanilides
Received: 31 January 2019 / Revised: 8 March 2019 / Accepted: 11 March 2019 / Published: 27 March 2019
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Abstract
Three different 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetamide (DOTAM) derivatives bearing as amide N-substituents phenyl, p-methoxyphenyl and p-ethylbenzoate groups were synthesized and the 1H and 17O NMR relaxometric behaviour of the Gd(III)-chelates and chemical exchange saturation transfer (CEST) effect of the Eu(III) complexes [...] Read more.
Three different 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetamide (DOTAM) derivatives bearing as amide N-substituents phenyl, p-methoxyphenyl and p-ethylbenzoate groups were synthesized and the 1H and 17O NMR relaxometric behaviour of the Gd(III)-chelates and chemical exchange saturation transfer (CEST) effect of the Eu(III) complexes were evaluated. The electronic properties of the substituents were shown to strongly influence the coordinated water exchange rate (kex), resulting in five times faster kex for the electron donating phenylmethoxy group compared to the electron withdrawing ethylbenzoate group. Full article
(This article belongs to the Special Issue MRI Contrast Agents)
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Open AccessArticle
Understanding Factors that Control the Structural (Dis)Assembly of Sulphur-Bridged Bimetallic Sites
Received: 19 February 2019 / Revised: 13 March 2019 / Accepted: 13 March 2019 / Published: 27 March 2019
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Abstract
Bimetallic structures of the general type [M2(µ-S)2] are omnipresent in nature, for biological function [M2(µ-S)2] sites interconvert between electronically distinct, but isostructural, forms. Different from structure-function relationships, the current understanding of the mechanism of formation [...] Read more.
Bimetallic structures of the general type [M2(µ-S)2] are omnipresent in nature, for biological function [M2(µ-S)2] sites interconvert between electronically distinct, but isostructural, forms. Different from structure-function relationships, the current understanding of the mechanism of formation and persistence of [M2(µ-S)2] sites is poorly developed. This work reports on bimetallic model compounds of nickel that interconvert between functional structures [Ni2(µ-S)2]+/2+ and isomeric congeners [2{κ-S–Ni}]2+/+, S = Aryl-S, in which the nickel ions are geometrically independent. Interconversion of the two sets of structures was studied quantitatively by UV–VIS absorption spectroscopy and cyclic voltammetry. Assembly of the [Ni2(µ-S)2]+ core from [2{κ-S–Ni}]+ is thermodynamically and kinetically highly preferred over the disassembly of [Ni2(µ-S)2]2+ into [2{κ-S–Ni}]2+. Labile Ni-η2/3-bonding to aromatic π-systems of the primary thiophenol ligand is critical for modeling (dis)assembly processes. A phosphine coligand mimics the role of anionic donors present in natural sites that saturate metal coordination. Three parameters have been identified as critical for structure formation and persistence. These are, first, the stereoelectronic properties of the metals ions, second, the steric demand of the coligand, and, third, the properties of the dative bond between nickel and coligand. The energies of transition states connecting functional and precursor forms have been found to depend on these parameters. Full article
(This article belongs to the Special Issue Binuclear Complexes)
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