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The hydrolytically stable dioxime ligand (2Z-6Z)-piperidine-2,6-dione (H3pidiox) acts as a strong chelator mainly with hard metals in high oxidation states, a pre-requisite for potential applications in metal sequestering processes from aqueous solutions. Reaction of ZrCl4 with H3pidiox in methanol gives the mononuclear compound [ZrIV(η1,η1,η2-H2pidiox-O,N,O′)2(OH2)2]Cl2·H2O·CH3OH (1), while the same reaction mixture in the presence of KOH gave the pentanuclear ZrOC [Zr IV5 (μ2-OH)4(OH2)4(μ2–η1,η1,η2-Hpidiox-O,N,O′)4(η1,η1,η1-HpidioxO,N,O′)4]·5KCl·3CH3OH·8H2O (2). Compound 1 is formed at very acidic pH = 0, and the pentanuclear ZrOC 2 at higher pH values (pH = 2). Compounds 1 and 2 were characterized by single crystal X-ray structure analysis, multi-nuclear NMR spectroscopy and ESI-MS spectrometry. The single crystal X-ray structure analysis of 1 revealed a mononuclear zirconium(IV) compound containing an eight-coordinate zirconium atom bound to two singly deprotonated H2pidiox− ligands and two water molecules in a severely distorted bicapped octahedral geometry. The pentanuclear ZrOC 2 constitutes the second example of a Zr5 cluster to be reported and the first one in which the four zirconium atoms are arranged in a tetrahedral arrangement with the fifth occupying the center of the tetrahedron. 1D and 2D NMR spectroscopies of the acidic CD3OD solutions of complex 1 reveal a fast equilibrium between 1 and 2. Addition of KOH into a CH3OH solution of 2 results in the controlled fast transformation of 2 to an asymmetric hexanuclear ZrOC 3 as evidenced by the NMR and real-time ESI-MS solution studies. Further addition of KOH to the solution of 3 leads to the ZrOC 4, and on the basis of NMR and ESI-MS data and in comparison with the known hexanuclear titanium(IV)/H3pidiox cluster, it is concluded that the cluster 4 should have a hexanuclear structure. Electrospray ionization mass spectrometry (ESI-MS) demonstrated not only the structural stability 1 and 2 in solution, but also revealed the reversible pH driven dis-assembly/re-assembly process between the monomeric 1 and the pentanuclear ZrOC 2. [ABSTRACT FROM AUTHOR]

The chiral dicobalt(II) complex [CoII2(μ2-L)2] (1) (H2L = N2,N6-di(quinolin-8-yl)pyridine-2,6-dicarboxamide) and its tert-butyl analogue [CoII2(μ2-LBu)2] (2) were synthesized and structurally characterized. Addition of one equivalent of AgSbF6 to the dichloromethane solution of 1 and 2 resulted in the isolation of the mixed-valent dicobalt(III , II) species [CoIIICoII(μ2-L)2]SbF6 (3) and [CoIIICoII(μ2-LBu)2]SbF6 (4). Homovalent 1 and 2 exhibited catalytic activity towards proton reduction in the presence of acetic acid (AcOH) as the substrate. The complexes are stable in solution while their catalytic turnover frequency is estimated at 10 and 34.6 h−1 molcat−1 for 1 and 2, respectively. Calculations reveal one-electron reduction of 1 is ligand-based, preserving the dicobalt(II) core and activating the ligand toward protonation at the quinoline group. This creates a vacant coordination site that is subsequently protonated to generate the catalytically ubiquitous Co(III) hydride. The dinuclear structure persists throughout where the distal Co(II) ion modulates the reactivity of the adjacent metal site by promoting ligand redox activity through spin state switching. [ABSTRACT FROM AUTHOR]

Heterometallic rare earth transition metal compounds of dithioxalate (dto)2–, [NiII{(dto)LnIIITp2}2] (Ln = Y (1), Gd (2); Tp = hydrotris(pyrazol-1-yl)borate) were synthesised. The Lewis acidic rare earth ions are bound to the dioxolene and chemical reduction of 1 and 2 with cobaltocene yielded [CoCp2]+[NiII{(dto)LnIIITp2}2]Ṗ− Ln = Y (3), Gd (4). The reduction is ligand-based and 3 and 4 are the first examples of both molecular and electronic structural characterisation of the dithiooxalato radical (dto)3Ṗ−. [ABSTRACT FROM AUTHOR]

Reaction of the cyclic ligand (2Z,6Z)-piperidine-2,6-dione dioxime with TiCl4 and KOH yielded the hexanuclear cluster K6[TiIV6(μ3-O)2(μ2-O)3(CH3O)6(μ2–η1,η1,η2-Hpidiox-O,N,O′)4(μ2–η1,η1,η2-pidiox-O,N,O′)2]·7.5CH3OH possessing a new {Ti6O5} structural motif. The cluster core {Ti6O5} is wrapped by external tripodal imide dioxime ligands, showing good solubility and stability and thus, allowing its solution to be studied by means of electrospray ionization mass spectrometry, electrochemistry and 2D NMR, c. w. EPR and UV-vis spectroscopies. Density Functional Theory (DFT) calculations reveal that the cyclo-Ti3 metallic cores exhibit metallaromaticity which is expected to contribute to the stabilization of this system. [ABSTRACT FROM AUTHOR]

The activation of dioxygen by metal ions is critical in chemical and bio-chemical processes. A scientific challenge is the elucidation of the activation site of dioxygen in some copper metalloproteins, which is either the metal center or the substrate. In an effort to address this challenge, we prepared a series of new copper(ii) complexes (1·2H2O, 2·CH3OH, 3) with bio-inspired amidate ligands and investigated their activity towards dioxygen activation. The secondary amine group ligated to copper(ii) of the complex 1·2H2O in methyl alcohol is oxidized (2e−) by air dioxygen in a stepwise fashion to an imine group, affording complex 2. The copper(ii) complex 2 in methyl alcohol induces the 4e− oxidation by air dioxygen of the imine functionality ligated to copper(ii) to an azinate group, resulting in the isolation of a dinuclear azinate copper(ii) compound (4). Experimental and computational studies, including X-band c. w. EPR, UV-vis and ESI-MS spectroscopy and density functional theory computations, indicate a direct attack of the dioxygen on the –HC=N– group ligated to copper(ii), and a possible mechanism of the oxidation of the –HC=N– functionality ligated to copper(ii) to an azinate group is provided. This unprecedented activation of dioxygen by a copper substrate paves the way for further exploration of the O2 activation mechanisms in enzymes and the development of effective catalysts in O2-involved green organic synthesis. [ABSTRACT FROM AUTHOR]

Utilization of [Mo2S2O2(H2O)6]2+ and a tellurite anion led to the formation of three new clusters, 1–3, with unique structural features. The tellurite anion not only templated the formation of [(Mo2O2S2)4(TeO3)(OH)9]3−1 and [(Mo2O2S2)12(TeO3)4(TeO4)2 (OH)18]10−3, but also the in situ generation of two different types of dimeric {Te2O6} based moieties induced the spontaneous assembly of the chiral [(Mo2O2S2)10(TeO3)(Te2O6)2(OH)18]8− anionic cluster, 2. [ABSTRACT FROM AUTHOR]

In recent years, great attention has been dedicated to the development of heterogeneous base catalysts providing a green and sustainable process in benign aqueous media. Herein, the ionic liquid modified layered double hydroxide (LDH) based catalysts of LDH-IL-Cn (n = 4, 8, 12) were prepared by adopting an exfoliation/assembly strategy, in which the ionic liquids (ILs) were covalently anchored onto the surface of LDH layers. The resulting LDH-IL-Cn were characterized by FT-IR, solid-state 13C NMR, 29Si CP/MAS NMR, 27Al-MAS NMR, XRD, TG-DTA, BET, XPS, SEM, CO2-TPD, contact angle experiments, etc. The catalytic performance of LDH-IL-C12 for the Knoevenagel condensation of a variety of aldehydes with ethyl cyanoacetate/malononitrile in H2O at room temperature showed excellent yields and selectivities. Moreover, the base catalyst of LDH-IL-C12 can be easily recycled and reused for at least 5 times without the decrease of its catalytic efficiency. The scaled-up experiments revealed that the catalyst retained its efficiency and robustness. [ABSTRACT FROM AUTHOR]

Deep desulfurization is a challenging task and global efforts are focused on the development of new approaches for the reduction of sulfur-containing compounds in fuel oils. In this work, we have proposed a new design strategy for the development of deep desulfurization heterogeneous catalysts. Based on the adopted design strategy, a novel composite material of polyoxometalate (POM)-based ionic liquid-grafted layered double hydroxides (LDHs) was synthesized by an exfoliation/grafting/assembly process. The structural properties of the as-prepared catalyst were characterized using FT-IR, XRD, TG, NMR, XPS, BET, SEM and HRTEM. The heterogeneous catalyst exhibited high activity in deep desulfurization of DBT (dibenzothiophene), 4,6-DMDBT (4,6-dimethyldibenzothiophene) and BT (benzothiophene) at 70 °C in 25, 30 and 40 minutes, respectively. The catalyst can be easily recovered and reused at least ten times without obvious decrease of its catalytic activity. Such excellent sulfur removal ability as well as the cost efficiency of the novel heterogeneous catalyst can be attributed to the rational design, where the spatial proximity of the substrate and the active sites, the immobilization of ionic liquid onto the LDHs via covalent bonding and the recyclability of the catalyst are carefully considered. [ABSTRACT FROM AUTHOR]

Two nanosized 2.6 nm FeIII substituted polyoxotungstates [FeIII13P8W60O227(OH)15(H2O)2]30- (1) and [FeIII13P8W60O224(OH)12(PO4)4]33- (2) are presented herein. Both clusters are synthesized from the reactions of trilacunary polyoxotungstate precursor [α-P2W15O56]12- and FeCl3 under strict pH control at atmospheric pressure. The compounds are fully characterised in the solid state (FTIR and single-crystal XRD, elemental and thermogravimetric analyses), solution (cyclic voltammetry and UV-Vis spectroscopy) and in the gas phase (ESI-MS). An {FeIII 13} core is present in both clusters which can be described as Archimedean solids (truncated tetrahedron, 1; elongated cuboctahedron, 2). 1 shows iron delivery properties coupled to a K+-triggered transformation of the {Fe13} core to a {K-Fe12} core in solution. Cyclic voltammetry shows the presence of independent W- and Fe-centred redox processes that support the stability of the clusters in solution. ESI-MS analyses confirm further the stability of 1 and 2 in the gas phase. [ABSTRACT FROM AUTHOR]

Two nanosized 2.6 nm FeIII substituted polyoxotungstates [FeIII13P8W60O227(OH)15(H2O)2]30- (1) and [FeIII13P8W60O224(OH)12(PO4)4]33- (2) are presented herein. Both clusters are synthesized from the reactions of trilacunary polyoxotungstate precursor [α-P2W15O56]12- and FeCl3 under strict pH control at atmospheric pressure. The compounds are fully characterised in the solid state (FTIR and single-crystal XRD, elemental and thermogravimetric analyses), solution (cyclic voltammetry and UV-Vis spectroscopy) and in the gas phase (ESI-MS). An {FeIII 13} core is present in both clusters which can be described as Archimedean solids (truncated tetrahedron, 1; elongated cuboctahedron, 2). 1 shows iron delivery properties coupled to a K+-triggered transformation of the {Fe13} core to a {K-Fe12} core in solution. Cyclic voltammetry shows the presence of independent W- and Fe-centred redox processes that support the stability of the clusters in solution. ESI-MS analyses confirm further the stability of 1 and 2 in the gas phase. [ABSTRACT FROM AUTHOR]

Two titanium embedded polyoxometalates with unprecedented structural features are presented: a monotitanium containing tungstoantimonate Na13H3[TiO(SbW9O33)2]·33 H2O featuring a {TiO}2+moiety (1) and a hexatitanium containing tungstoarsenate K6[Ti4(H2O)10(AsTiW8O33)2]·30 H2O containing a {Ti4(H2O)10}16+moiety (2). Both compounds have been fully characterised by single crystal X-ray diffraction, elemental analysis, IR and TGA. 1is constructed from two α-B-{SbIIIW9O33} fragments linked by five sodium cations and an unprecedented square pyramidal Ti(O)O4group with a terminal TiO bond, and 2exhibits a Krebs-type structure composed of two {AsTiW8O33} fragments, where one W(vi) centre has been substituted for a Ti(iv) centre in each, fused together viaa belt of four additional Ti(iv) centres. This system represents the tungsten Ti-incorporated polyoxoanion with one of the highest Ti : W ratios so far reported. Additionally, 2could also be isolated as an n-tetrabutylammonium salt and has been further characterised by electrochemistry and electrospray ionisation (ESI) MS studies. Due to the unique nature of these systems, both have been fully investigated using DFT calculations yielding highly interesting results. Structure 1has been optimised with five sodium atoms in the belt position, which in addition to reducing the high charge of the cluster influence a stabilisation of the antimony lone pairs. Electrostatic potential calculations highlight the high electronegativity of the terminal oxygen on the titanium centre, enhancing real potentiality as a reactive site for catalysis. [ABSTRACT FROM AUTHOR]

Four iso-structural triple Wells-Dawson-type phosphotungstate compounds incorporating six transition metal ion linkers are presented of the form [(M2P2W16O60)3]24−/30−, 1–4, where M = Co, Mn, Fe, Ni respectively and compounds 3and 4are revealed for the first time uniting a family of isostructural clusters. Further, a comparative study of the solid-state arrangements of polyoxoanions 1–4is presented as well as an in-depth discussion of the synthetic conditions which give rise to the formation of the clusters. Each cluster subunit displays an unprecedented diequatorial substitution pattern facilitating the combination of three such units into a trimer, creating central cavities in the range 6.61–6.82 Å. The solid state arrangements of polyoxoanions 1, 3and 4are similar, but as a result of the relevant synthetic approaches, they differ greatly from that of 2. Electrochemical analysis of the new structures is detailed revealing that polyoxoanion 4shows potential as an electrocatalyst in the reduction of nitrites. [ABSTRACT FROM AUTHOR]