Synthesis of ω-Hydroxy Fatty Acid Alkyl Esters by Macrocyclic Lactones Alcoholysis Catalyzed by Homoleptic and Heteroleptic Zinc Aryloxides.

A series of zinc aryloxides, [Zn(sal-Me)]⋅2.5(CH) (1), [Zn(sal-Me)]⋅CHCl (2), [Zn(μ-OR)(sal-R)] (3) (for R=Me (0.51), Et (0.

Recycling primary lithium batteries using a coordination chemistry approach: recovery of lithium and manganese residues in the form of industrially important materials.

In this study, we have investigated the potential use of post-consumer primary lithium metal batteries (LMBs) commonly used in portable electronic devices to recover lithium and manganese in the form of industrially important materials. A direct reaction of lithium-containing electronic waste with a naturally sourced ester, methyl salicylate, combined with a wide range of aliphatic alcohols has been used as a general method for recovering lithium in the form of lithium aryloxides of different nuclearities [Li(OAr)(HOMe)] (1), [Li(OAr)(HOAr)] (2), [Li(OAr)(HOEt)] (3), [Li(OAr)(HO)] (4), [Li(OAr)(EGME)] (5), [Li(OAr)] (6-8) for ArOH = methyl salicylate (1, 2, 4, 6), ethyl salicylate (3, 7), 2-methoxyethyl salicylate (5, 8), and EGME = 2-methoxyethanol. The hydrolysis of 7 was then used to synthesize lithium salicylate [Li(Sal)(HO)] (10), which is an important antioxidant in the production of oils and grease.

Heterometallic 3d-4f Alkoxide Precursors for the Synthesis of Binary Oxide Nanomaterials.

In this study, a new method for the synthesis of heterometallic 3d-4f alkoxides by the direct reaction of metallic lanthanides (La, Pr, Nd, Gd) with MCl (M = Mn, Ni, Co) in 2-methoxyethanol was developed. The method was applied to the synthesis of the heterometallic oxo-alkoxide clusters [LnMn(μ-O)(μ-OR)(HOR)Cl] (Ln = La (), Nd (), Gd (); = 0, 2, 4); [PrM(μ-O)(μ-OR)(HOR)Cl] (M = Co (), Ni (); = 2, 4); and [LnMn(μ-OH)(μ-OR)(μ-OR)(μ-Cl)(HOR)Cl] (Ln = La () and Pr ()). Mechanistic investigation led to the isolation of the homo- and heterometallic intermediates [Pr(μ-OR)(μ-Cl)(HOR)Cl] (), [Co(μ-OR)(HOR)Cl] (), [Ni(μ-OR)(HOEt)Cl] (), [Mn(μ-OR)(HOR)(HOEt)Cl] (), and [Nd(HOR)Cl][CoCl] ().

Use of heterometallic alkali metal-magnesium aryloxides in ring-opening polymerization of cyclic esters.

In this work, alkali metal-magnesium aryloxides [MgLi(MesalO)] (1), [MgNa(MesalO)(THF)] for = 2 or 4 (2), and [MgK(MesalO)(THF)] (3) derived from the reaction of MgBu and BuLi, metallic Na or K with methyl salicylate (MesalOH) were used as molecular platforms for the synthesis of new heterometallic compounds [MgLi(EtsalO)] (4), [MgK(EtsalO)] (5), [MgNaAl(MesalO)(OH)(MesalOH)(THF)(HO)] (6), and [MgNa(MesalO)(SalO)(THF)] (7) (EtsalOH = ethyl salicylate and SalOH = salicylic acid) by the reaction with EtOH, exposure to atmospheric moisture or addition of stoichiometric quantities of water. Compounds 4 and 5 were synthesized by transesterification of 1 and 3. Cluster 6 was formed haphazardly by exposing a THF solution of 2 derived using MgBu stabilized with 1 wt% AlEt to atmospheric moisture.

Use of group 13 aryloxides for the synthesis of green chemicals and oxide materials.

In this work, group 13 metal aryloxides [Al(MesalO)] (1), [MeGa(MesalO)] (2), [AlLi(MesalO)] (3) and [MeGaLi(MesalO)(THF)] (4) were obtained by the reaction of methyl salicylate (MesalOH) with group-13 alkyls MMe (for M = Al, Ga) or their combination with BuLi in a THF/alcohol solution. The direct reaction of MMe (for M = Al, Ga) and MesalOH (1 : 3) led to compound 1 or 2, respectively. When the same reactions were carried out with additional BuLi, the heterometallic compound 3 or the mixture of 4 and [Li(MesalO)] (5) was obtained.

Heterometallic Group 4-Lanthanide Oxo-alkoxide Precursors for Synthesis of Binary Oxide Nanomaterials.

In this study, an efficient procedure for the synthesis of uncommon group 4-lanthanide oxo-alkoxide derivatives was developed. Heterometallic clusters with the structures [LaTi(μ-O)(μ-OEt)(μ-OEt)(OEt)(Cl)(HOEt)] (), [LaZr(μ-O)(μ-OEt)(μ-Cl)(OEt)(HOEt)(Cl)] (), [LaHf(μ-O)(μ-OEt)(μ-Cl)(OEt)(HOEt)(Cl)] (), [NdTi(μ-O)(μ-OEt)(μ-OEt)(OEt)(HOEt)(Cl)] (), [NdZr(μ-O)(μ-OEt)(μ-Cl)(OEt)(HOEt)(Cl)] (), and [NdHf(μ-O)(μ-OEt)(μ-Cl)(OEt)(HOEt)(Cl)] () were synthesized via the reaction of a metallocene dichloride, CpM'Cl (where M' = Ti, Zr, and Hf), and metallic lanthanum or neodymium in the presence of excess ethanol. This procedure gave crystalline precursors with molecular stoichiometries suitable for obtaining group 4-lanthanide oxide materials.

Convenient Route to Heterometallic Group 4-Zinc Precursors for Binary Oxide Nanomaterials.

In this study, simple and efficient synthetic routes to a family of uncommon group 4-zinc heterometallic alkoxides were developed. Single-source molecular precursors with the structures [CpTiZn(μ,η-OR)(THF)Cl] (), [ZrZn(μ-O)(μ,η-OR)(μ-OH)(μ,η-OR)(μ,η-OR)Cl] (), and [HfZn(μ-O)(μ,η-OR)(μ-OH)(μ,η-OR)(μ,η-OR)Cl] () were prepared via reduction of CpTiCl with metallic zinc or protonolysis of the metal-cyclopentadienyl bond in CpM'Cl (M' = Zr or Hf) in the presence of 2-methoxyethanol (ROH) and Zn(OR). This synthetic route enables the creation of compounds with well-defined molecular structures and therefore provides precursors suitable for obtaining group 4-zinc oxides.

Use of lithium aryloxides as promoters for preparation of α-hydroxy acid esters.

In this work, a hexanuclear lithium compound, [Li6(MesalO)6] (1), supported by a chelating ligand, namely methyl salicylato (MesalOH), was used as a precursor for preparation of the monomeric lithium aryloxides [Li(MesalO)(MesalOH)] (2) and [Li(MesalO)(MeOH)2] (3) via reactions with MesalOH or MeOH. These aryloxides were characterized by single-crystal X-ray diffraction, and spectroscopic and other analytical methods. The diffusion-ordered 1H NMR measurements revealed the retention of solid-state structures of 1 and 2 in THF-d8 solution.

A new, simple, and efficient strategy for the preparation of active antifungal biodegradable materials via ring-opening polymerization of l-lactide with zinc aryloxides.

In this work, zinc aryloxides supported by monodentate hydroxybiphenyls [ArOH: ortho-phenylphenol (o-XenOH), meta-phenylphenol (m-XenOH), or para-phenylphenol (p-XenOH] and N,N,N',N'-tetramethylethylenediamine (TMEDA) were used to develop active polymeric materials for antifungal agents for agricultural use. The direct reaction of ligand precursor ArOH with ZnEt2 (1 : 2) in a toluene/TMEDA mixture (1 : 10) afforded a series of three isostructural monomeric compounds, namely [Zn(o-XenO)2(TMEDA)] (1), [Zn(m-XenO)2(TMEDA)] (2), and [Zn(p-XenO)2(TMEDA)] (3). These were characterized by single-crystal X-ray diffraction, and spectroscopic and other analytical methods.

Molecular Routes to Group IV Magnesium and Calcium Nanocrystalline Ceramics.

The effect of alkaline-earth-metal alkoxides on the protonolysis of CpM'Cl (M' = Ti, Zr, Hf; Cp = cyclopentadiene) was investigated. This approach enabled the design of compounds with well-defined molecular structures to generate high-purity binary metal oxides. Single-source molecular precursors with structures of [MM'(μ-OEt)(μ-OEt)(OEt)(EtOH)] with M = Mg and M' = Ti (1), Zr (2), and Hf (3), [CaTi(μ-O)(μ-O)(μ-OEt)(OEt)(EtOH)Cl] (4), and [MM'(μ-O)(μ-OEt)(OEt)(EtOH)Cl] with M = Ca and M' = Zr (5) and Hf (6) were prepared via elimination of the cyclopentadienyl ring from CpM'Cl as CpH in the presence of M(OEt) and ethanol (EtOH) as a source of protons.

Impact of Group 13 Metals on CpTiCl Reduction and Structural Characterization of Resulting Compounds.

The aim of the current study was to examine the effects of group 13 metals on CpTiCl reduction in the presence of 2-methoxyethanol (MeOEtOH) or ethanol (EtOH) and the compositions of the resulting products. Direct reaction of CpTiCl and M [Al, Al (Fe contaminated), Ga, In] in toluene/alcohol for 2 h gave a new family of uncommon homo- and heterometallic compounds: [CpTiAl(μ,η-OEtOMe)Cl][Ti(μ,η-OEtOMe)(η-OEtOMe)Cl] (1), [CpTiAl(μ,η-OEtOMe)Cl]Cl (2), [CpTiAl(μ,η-OEtOMe)Cl][CpTi(η-HOEtOMe)][FeCl] (3), [CpTi(η-HOEtOMe)][GaCl][Cl] (4), [CpTi(μ-OEt)(OEt)][GaCl] (5), [CpTi(μ,η-OEtOMe)Cl] (6), and [CpTi(μ,η-OEtOMe)(μ-OEtOMe)Cl] (7). The reaction with indium for 48 h resulted in isolation of [TiIn(μ,η-OEtOMe)(OEtOMe)Cl] (8), [In(μ-OEtOMe)(HOEtOMe)Cl] (9), and [Ti(OEtOMe)] (10).

Synthesis of Aluminosilicates Containing a Ba(Sr)-O-Al-O-Si Arrangement of Natural Feldspar Mineral.

We report a facile route to multicomponent complexes of [M{(μ-ddbfo)Al(OSiR)}] (M = Ba, Sr; ddbfoH = 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; R = Ph, OBu) as new efficient single-source routes to barium and strontium celsian feldspar Ba(Sr)AlSiO. The resulting complexes were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray diffraction. These compounds calcined at 1100 °C to give porous material Ba(Sr)AlSiO·2SiO as an amorphous silica matrix containing spherical oxide nanocrystals of celsian feldspar of ca.

Unexpected Reactions between Ziegler-Natta Catalyst Components and Structural Characterization of Resulting Intermediates.

In this work, we investigated precursors and procatalysts with well-defined crystal structures and morphologies in Ziegler-Natta systems to improve our understanding of the nature of the active metal sites. Molecular cluster precursors such as [Mg4Ti3(μ6-O)(μ3-OH)3(μ-OEt)9(OEt)3(EtOH)3Cl3], [Mg4Ti3(μ6-O)(μ3-OH)(μ3-OEt)2(μ-OEt)9(OEt)3(EtOH)3Cl3], and [Mg6Ti4(μ6-O)2(μ3-OH)4(μ-OEt)14(OEt)4(EtOH)2Cl2] were prepared via simple elimination of the cyclopentadienyl ring from Cp2TiCl2 as CpH in the presence of magnesium metal and ethanol. Titanocene dichloride acts as both a source of titanium and a magnesium-chlorinating agent.

Alkaline Earth Metal Zirconate Perovskites MZrO3 (M=Ba(2+), Sr(2+), Ca(2+)) Derived from Molecular Precursors and Doped with Eu(3+) Ions.

The effect of alkaline earth metal alkoxides on the protonation of zirconocene dichloride was investigated. This approach enabled the design of compounds with preset molecular structures for generating high-purity binary metal oxide perovskites MZrO3 (M=Ba(2+), Sr(2+), Ca(2+)). Single-source molecular precursors [Ba4 Zr2 (μ6 -O)(μ3 ,η(2)-OR)8 (OR)2(η(2) -HOR)2 (HOR)2 Cl4], [Sr4 Zr2 (μ6 -O)(μ3 ,η(2)-OR)8 (OR)2 (HOR)4 Cl4], [Ca4 Zr2 (μ6-O)(μ3 ,η(2)-OR)8 (OR)2 Cl4], and [Ca6 Zr2 (μ2 ,η(2)-OR)12 (μ-Cl)2 (η(2) -HOR)4 Cl6 ]⋅8 CH2 Cl2 were prepared via elimination of the cyclopentadienyl ring from Cp2 ZrCl2 as CpH in the presence of M(OR)2 and alcohol ROH (ROH=CH3OCH2 CH2OH) as a source of protons.

Fluphenazine: from an isolated molecule to its interaction with lipid bilayers.

Fluphenazine (FPh) belongs to the phenothiazine family of compounds and exhibits a wide variety of biological effects, including antimutagenic, proapoptotic, antiproliferative and anti-multidrug resistance (MDR) activities. The ability of FPh to interact with lipid membranes can have a significant impact on its biological activities. However, the mechanisms involved in the interaction of FPh with lipid membranes are poorly understood.

Probing the role of π interactions in the reactivity of oxygen species: a case of ethylzinc aryloxides with different dispositions of aromatic rings toward the metal center.

Ethylzinc derivatives of ortho-hydroxybiphenyl and 2,6-diphenylphenol that bear different nuclearity and dispositions of aromatic rings toward the metal center were synthesized and structurally characterized in the solid state and solution. This family of well-defined compounds was examined as a model system for the activation of dioxygen mediated by using complexes that feature lack of a redox-active metal center. Experimental and theoretical studies indicate an essential role in the oxygenation process of intramolecular interactions that involve aromatic subunits.

Transformation of barium-titanium chloro-alkoxide compound to BaTiO3 nanoparticles by BaCl2 elimination.

In this Article, we present how the molecular precursor of binary oxide material having an excess of alkali earth metal can be transformed to the highly phase pure BaTiO3 perovskite. Here, we synthesized and compared two barium-titanium complexes with and without chloride ligands to determine the influences of different ligands on the phase purity of binary oxide nanoparticles. We prepared two barium-titanium complexes, i.

Probing secondary coordination sphere influence on the oxygenation of zinc alkyls: formation of a unique zinc peroxide species.

Reactions of ethylzinc derivatives of o-hydroxybiphenyl with O2 were investigated. The study revealed an essential role in the oxygenation process of intra-molecular interactions involving aromatic rings and provided a unique aryloxide (hydroxide) Zn8(OAr)8(OH)6(O2) cluster with an encapsulated peroxide species.

Zinc complexes supported by methyl salicylato ligands: synthesis, structure, and application in ring-opening polymerization of L-lactide.

Two novel zinc alkoxides supported by chelating methyl salicylato (MesalO; MesalOH = methyl salicylate) ligands were successfully synthesized and characterized. Reaction of MesalOH with ZnEt2 (2:1) gives a tetranuclear cluster [Zn(MesalO)2]4 (1), which by addition of pyridine is transformed to the mononuclear compound [Zn(MesalO)2(py)2] (2). Compounds 1 and 2 were characterized by elemental analysis, NMR, IR, and single crystal X-ray diffraction.

Dieth-yl(μ3-2-methyl-4-oxo-4H-pyran-3-olato-κ(4) O (3),O (4):O (3):O (3))tris-(μ2-2-methyl-4-oxo-4H-pyran-3-olato-κ(3) O (3),O (4):O (3))trizinc toluene disolvate.

The title compound, [Zn3(C2H5)2(C6H5O3)4]·2C7H8, crystallizes with one complex mol-ecule solvated by two mol-ecules of toluene in the asymmetric unit. The Zn(II) ions are coordinated by two terminal ethyl (Et) groups and four maltolate ligands, which act as μ3- and μ2-bridges. The metal atoms are arranged in an incomplete cubane Zn3O4 core structure, derived from one EtZnO3 tetra-hedron, one EtZnO4 bipyramid and one ZnO6 octa-hedron, sharing common corners.

A dinuclear zinc complex containing a diamond-core geometry: [Zn2(μ2-GueO)2(GueO)2(py)2]·0.5(toluene) (GueOH is guethol).

The title zinc alkoxide, bis(μ-2-ethoxyphenolato)-κ(3)O(1),O(2):O(1);κ(3)O(1):O(1),O(2)-bis[(2-ethoxyphenolato-κ(2)O(1),O(2))(pyridine-κN)zinc(II)] toluene hemisolvate, [Zn2(C8H9O2)4(C5H5N)2]·0.5C7H8, crystallizes with two independent complex molecules located on inversion centres and one independent toluene solvent molecule disordered about an inversion centre. The Zn(II) atoms are six-coordinated in distorted octahedral geometries with O5N donor sets.

Interaction of piperidin derivative of Mannich base with DPPC liposomes.

The long chain Mannich bases, especially with the piperidine and morpholine groups, display very promising antimicrobial activity. In order to extend our knowledge on their impact on biological systems, we examined the interactions of the 5-pentadecyl-2-((piperidin-1-yl)methyl)phenol (PPDP) with model lipid membrane by means of differential scanning calorimetry (DSC) and fluorescence measurements. The small unilamellar vesicles of dipalmitoylophosphatidylcholine (DPPC) with different piperidine Mannich base concentration were investigated as a function of the increase of temperature.

Two tetranuclear zinc clusters, [Zn4(μ3-OEt)2(μ2-MalO)4Et2] and [Zn4(μ3-GueO)2(μ2-GueO)2(μ2-MalO)2(MalO)2]·2C7H8, containing defective dicubane core geometries (MalOH is maltol and GueOH is guethol).

The zinc alkoxide molecules in di-μ(3)-ethanolato-diethyltetrakis(μ(2)-2-methyl-4-oxo-4H-pyran-3-olato-κ(3)O(3),O(4):O(3))tetrazinc(II), [Zn(4)(C(2)H(5))(2)(C(2)H(5)O)(2)(C(6)H(5)O(3))(4)], (I), and bis(μ(3)-2-ethoxyphenolato-κ(4)O(1),O(2):O(1):O(1))bis(μ(2)-2-ethoxyphenolato-κ(3)O(1),O(2):O(1))bis(μ(2)-2-methyl-4-oxo-4H-pyran-3-olato-κ(3)O(3),O(4):O(3))bis(2-methyl-4-oxo-4H-pyran-3-olato-κ(2)O(3),O(4))tetrazinc(II) toluene disolvate, [Zn(4)(C(6)H(5)O(3))(4)(C(8)H(9)O(2))(4)]·2C(7)H(8), (II), lie on crystallographic centres of inversion. The asymmetric units of (I) and (II) contain half of the tetrameric unit and additionally one molecule of toluene for (II). The Zn(II) atoms are four- and six-coordinated in distorted tetrahedral and octahedral geometries for (I), and six-coordinated in a distorted octahedral environment for (II).

Fluphenazine dihydro-chloride dimethanol solvate.

In the title compound {systematic name: 1-(2-hy-droxy-eth-yl)-4-[3-(2-trifluoro-methyl-10H-phenothia-zin-10-yl)prop-yl]piperazine-1,4-diium dichloride dimethanol disolvate}, C(22)H(28)F(3)N(3)OS(2+)·2Cl(-)·2CH(3)OH, the dihedral angle between the planes of the two outer benzene rings of the tricyclic phenothia-zine system is 46.91 (13)°. The piperazine ring adopts a chair conformation.

Nucleotide-amino acid interactions in the L-His-IMP.MeOH.H(2)O complex.

In the crystal structure of the methanol-solvated monohydrated complex of L-histidine (His) with inosine 5'-monophosphate (IMP), namely L-histidinium inosine-5'-phosphate methanol solvate monohydrate, C(6)H(10)N(3)O(2)(+).C(10)H(12)N(4)O(8)P(-).CH(3)OH.