Improving the Halogen–Magnesium Exchange by using New Turbo-Grignard Reagents

This Minireview describes the scope of the halogen–magnesium exchange. It shows that the use of the turbo-Grignard reagent (iPrMgCl⋅LiCl) greatly enhances the rate of the Br– and I–Mg exchange. Furthermore, this magnesium reagent allows the performance of a fast sulfoxide–magnesium exchange. Also, the use of sBuMgOR⋅LiOR (R=2-ethylhexyl) enables a Br–Mg exchange in toluene leading to various Grignard reagents in toluene. Additionally, the new exchange reagent sBu₂Mg⋅2 LiOR (R=2-ethylhexyl) further increases the rate of the halogen–magnesium exchange allowing one to perform a chlorine–magnesium exchange for aromatic chlorides bearing an ortho-methoxy substituent in toluene.     

MNDO method for calculations of magnesium clusters

A new set of parameters for the magnesium atom has been developed within the MNDO method. In contrast to previously published parameters, the new parameters correctly describe molecules with different chemical natures: magnesium halides, organomagnesium compounds and the recently found small magnesium clusters Mg _n (n=2-8). The average errors in the calculated heats of formation and bond lengths of magnesium compounds, including clusters are: 10.7 kcal/mol and 0.167 Å, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1384–1388, August, 1994.     

The crystal and molecular structure of an ionic hydrazinium magnesium(II) complex with pyridazine-3,6-dicarboxylate and water ligands

The structure of hydrazinium magnesium(II) pyridazine-3,6-dicarboxylate comprises two univalent hydrogen hydrazine cations, a divalent di(aqua-O)bis(pyridazine-3,6-dicarboxylato-N,O) magnesium(II) anion and two solvate water molecules in the triclinic unit cell. The magnesium(II) ion is located on the center of symmetry. The coordination around the magnesium(II) ion is slightly distorted octahedral. The ligand molecules are coplanar. Their N,O bonding moieties coordinated to the metal ion form the equatorial plane of the distorted octahedron (Mg–O 2.062?Å, Mg–N 2.176?Å) with two water ligands in the trans axial sites (Mg–O 2.047?Å).     

Study of MgO/MgAc2 catalyst activity inn-butane pyrolysis

Distributions ofn-butane pyrolysis products and activities of catalysts have been analyzed. The catalysts based on magnesium oxide was preparedvia modification with magnesium acetate.n-Butane decomposition is shown to be accelerated due to active surface centers of at least two types.     

An enzymatic method for determining magnesium

The effect of magnesium ions on the catalytic activity of alkaline phosphatases from three different sources in the reaction of p-nitrophenyl phosphate hydrolysis was studied. It was found that magnesium in concentrations of 0.6 ng/mL-20 µg/mL significantly activated alkaline phosphatase from chicken intestine; in higher concentrations (0.02–0.2 mg/mL), it weakly activated the enzyme from E. coli and had no effect on the catalytic activity of the enzyme from the small intestine of the Greenland seal. The strongest activating effect was observed in a Tris-HCl buffer solution at pH 9.8. The activating effect of magnesium on alkaline phosphatase from chicken intestine was used as the basis for developing a highly sensitive and selective enzymatic procedure for determining magnesium (0.6–6.0 ng/mL; RSD = 4% at c _min; n = 5) by spectrophotometrically monitoring the rate of enzymatic reaction. The developed procedure was applied to the determination of magnesium in urine.__________Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 4, 2005, pp. 425–433.Original Russian Text Copyright © 2005 by Zhavoronkova, Muginova, Shekhovtsova.     

Synthesis of MgAPO-5 molecular sieves and their kinetic behavior for n-hexane cracking

Five magnesium substituted aluminophosphate molecular sieves (denoted as MgAPO-5 (a–e), AFI topology) with different magnesium contents were synthesized hydrothermally and characterized by XRD, ICP-AES, IR, and NH₃-TPD techniques. The characterization data show that the isomorphous substitution of magnesium for aluminum in the pure AFI framework results in MgAPO-5 (a–e) with weak and strong acid sites and that the number of strong acid sites linearly increases with increasing magnesium content (correlation coefficient: 0.9960). n-Hexane catalytic cracking over MgAPO-5 (a–e) was investigated at low conversions (≤5%) in a microflow fixed bed reactor. Under controlled conditions, the reaction was first order in both the n-hexane concentration and the magnesium content. The analysis of the kinetic parameters and the product selectivities suggests that the cracking transformation is effected by strong Mg(II)-related acid sites rather than weak ones and predominantly undergoes the monomolecular protolytic mechanism, which is consistently explained by a proposed kinetic model.     

Analyses of the temperature and pH effects on the complexation of magnesium and calcium in human blood plasma: an approach using artificial neural networks

The temperature and pH effects on the equilibrium of a blood plasma model have been studied on the basis of artificial neural networks. The proposed blood plasma was modeled considering two important metals, calcium and magnesium, and six ligands, namely, alanate, carbonate, citrate, glycinate, histidinate and succinate. A large data set has been used to simulate different concentrations of magnesium and calcium as a function of temperature and pH and these data were used for training the neural network. The proposed model allowed different types of analyses, such as the effects of pH on calcium and magnesium concentrations, the competition between calcium and magnesium for ligands and the effects of temperature on calcium and magnesium concentrations. The model developed was also used to predict how the variation of calcium concentration can affect magnesium concentrations. A comparison of neural network predictions against experimental data produced errors of about 3%. Moreover, in agreement with experimental measurements (Wang et al. in Arch. Pathol. 126:947–950, 2002; Heining et al. in Scand. J. Clin. Lab. Invest. 43:709–714, 1983), the artificial neural network predicted that calcium and magnesium concentrations decrease when pH increases. Similarly, the magnesium concentrations are less sensitive than calcium concentrations to pH changes. It is also found that both calcium and magnesium concentrations decrease when the temperature increases. Finally, the theoretical model also predicted that an increase of calcium concentrations will lead to an increase of magnesium concentration almost at the same rate. These results suggest that artificial neural networks can be efficiently applied as a complementary tool for studying metal ion complexation, with especial attention to the blood plasma analysis. Figure Artificial neural networks for predicting the behavior of calcium and magnesium as a function of pH and temperature in human blood plasma     

Complex Formation of Magnesium(II) with Octaaryltetraazaporphyrins in Pyridine

Complex formation of magnesium with octaphenyltetraazaporphyrin, octakis[p-(chloromethyl)phenyl]tetraazaporphyrin, and octakis[p-(dodecylsulfamoyl)phenyl]tetraazaporphyrin from corresponding ligands and magnesium acetate in pyridine and pyridine-diethylamine was studied. Increase in the basicity of the medium favors a much faster reaction. Some suggestions concerning the mechanism of the reaction were made.     

Synthesis of magnesium catecholate and <Emphasis Type="Italic">o</Emphasis>-semiquinone complexes by oxidation of the metal with 3,6-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-<Emphasis Type="Italic">o</Emphasis>-benzoquinone

Oxidation of amalgamated magnesium metal with 3,6-di-tert-butyl-o-benzoquinone (1) in different aprotic organic solvents afforded magnesium catecholate and bis-o-semiquinolate complexes. The catecholate derivatives of magnesium CatMgL₂ (Cat is the 3,6-di-tert-butyl-o-benzoquinone dianion, L = THF or Py) were synthesized in high yields in pyridine and tetrahydrofuran, respectively. The reactions in diethyl ether or dimethoxyethane produced hexacoordinated metal bis-o-semiquinolates SQ₂MgL_n (SQ is the 3,6-di-tert-butyl-o-benzoquinone radical anion, L = Et₂O, n = 2; L = DME, n = 1). The reaction with the use of toluene as the solvent gave a magnesium bis-o-semiquinolate complex containing the coordinated unreduced o-quinone molecule. The molecular structures of the [CatMgPy₂]₂ and SQ₂Mg·DME complexes were established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 92–98, January, 2007.     

Relationship between the level of essential metal elements in human hair and coronary heart disease

Studies on epidemics have demonstrated the relationship between coronary heart disease (CHD) and mineral substances, such as selenium, calcium, magnesium, sodium, potassium, copper, zinc, iron, manganese, and vanadium, in human bodies. In this study, instrumental neutron activation analysis (INAA) and flame atomic absorption spectrophotometry (FAAS) were applied to evaluate the levels of selenium, calcium, magnesium, sodium, potassium, copper, zinc, and iron in healthy individuals and CHD patients. Hair samples were collected from 42 healthy participants and 28 diagnosed CHD patients. Calcium, magnesium, copper, and zinc levels in healthy individuals are significantly higher than the levels found in the patients (p < 0.01). Calcium/selenium ratio is also significantly higher in healthy individuals (p < 0.05). Based on the possible synergies and/or antagonisms of elements and their absorption and metabolism, magnesium/calcium, zinc/copper, and sodium/potassium ratios showed positive relevance (p < 0.01).     

Bromination of Tetraazaporphine and Its β-Substituted Derivatives Using Pyridine as Solvent and Catalyst

The selectivity and degree of bromination of pyrrole rings in porphyrazine strongly depends on the brominating agent and solvent nature. The reaction of porphyrazine magnesium complex with molecular bromine and N-bromosuccinimide in pyridine gave magnesium complex of dibromotetraazaporphine. Increasing bromine substitution in porphyrazine enhances its acidic properties.     

Local Structure of Nanoscopic Magnesium Hydroxide ­Fluorides Studied by Natural Abundance 25Mg Solid State NMR Spectroscopy

Along with X‐ray diffraction measurements, ²⁵Mg solid state NMR experiments were performed in natural abundance at 9.4 T on crystalline and mechanically milled samples of MgO, Mg(OH)₂, MgF₂, and magnesium hydroxide fluorides Mg(OH)_xF_2–x prepared on mechanochemical and sol‐gel syntheses routes. In addition to single pulse and spin‐echo sequences, both static ¹H‐²⁵Mg CP and ¹⁹F‐²⁵Mg CP measurements allowed the registration of ²⁵Mg spectra in attractive short measurement times. Although an assignment of different magnesium species in magnesium hydroxide fluorides is only hardly possible, position and line shapes of ²⁵Mg spectra of magnesium hydroxide fluorides reflect chemically reliable trends. All samples studied here show a sixfold fluorine, oxygen, or mixed fluorine / oxygen coordination of magnesium, also in highly disordered samples.     

Extrapolation studies on adsorption of thorium and uranium at different solution compositions on soil sediments

Study on adsorption of thorium and uranium radionuclides by a soil sediment as a function of ionic composition of Ca, Mg and Na has been carried out. Experimentally determined slopes represents an average of adsorption on soil sediments having different relative affinities for thorium, uranium, calcium and magnesium. Both thorium and uranium were found to be adsorbed to ion-exchange sites together with calcium and magnesium cations as effective competitors An extrapolated equation for the distribution coefficientK _d was formed for both radionuclides thorium and uranium at the specified site where the soil sediments were sampled. The combined cation concentration of both calcium and magnesium in solution correlates linearly with the measuredK _d ^Th,U values.     

Low-temperature dehalogenation of benzyl halides with atomic magnesium in the3P state

Low-temperature reactions of benzyl halides with magnesium in the³P state proceed according to the radical mechanism accompanied by abstraction of the halogen atom by the biradical magnesium atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 147–151, January, 1999.     

Der Einbau von Magnesium in Liganden der Chlorophyll-Reihe mit (2,6-Di-t-butyl-4-methylphenoxy)magnesiumjodid

Introduction of Magnesium into Ligands of the Chlorophyll Series by (2,6-Di-t-butyl-4-methylphenoxy)magnesium Iodide Experimental details are given for the new method of introducing magnesium into porphinoid ligands by (2,6-di-t-butyl-4-methylphenoxy)magnesium iodide (1) , previously published in preliminary form [1]. Besides magnesium octaethylporphyrinate (14) , methyl pyrochlorophyllide a (10) , methyl chlorophyllide a (8) , and methyl bacteriochlorophyllide a (12) , the complexation of pheophytin a (2) to chlorophyll a (3) and of pheophytin b (4) to chlorophyll b (5) are described.     

Rapid analysis of cation-exchangeable property in acidic soil : III. Sensitive spectrophotometric determination of microgram amounts of exchangeable magnesium with xylidyl Blue I in the presence of cetyltrimethylammonium bromide (CTAB)

A simple and sensitive procedure for Spectrophotometric determination of exchangeable magnesium has been developed. At 0.15 – 0.375 N ammonia, magnesium reacts with xylidyl Blue I in the presence of CTAB to form a colored ternary complex, which has an absorption maximum at 524 nm. The molar absorption coefficient is 2.2 × 10⁴ liters · mol⁻¹ · cm⁻¹. The Beer rule will be valid for concentrations from 0 to 8 μg/20 ml magnesium. The method has been used for rapid determination of microgram amounts of exchangeable magnesium in acidic soil with good reproducibility.     

Alkaline‐Earth‐Promoted CO Homologation and Reductive Catalysis

Reaction between a β‐diketiminato magnesium hydride and carbon monoxide results in the isolation of a dimeric cis‐enediolate species through the reductive coupling of two CO molecules. Under catalytic conditions with PhSiH₃, an observable magnesium formyl species may be intercepted for the mild reductive cleavage of the CO triple bond.     

Determination of the Mg-Concentration Profile in Near-Surface Layers of Materials Using the 24Mg(α,p)27Al Nuclear Reaction

 The ²⁴Mg(α, p)²⁷ Al nuclear reaction was applied for the determination of the magnesium distribution in near-surface layers of materials. The cross sections of this reaction were determined in the energy region between 4.5 and 5.5 MeV in steps of 5 to 10 KeV (θ_lab : 158°) using thin magnesium films. The investigated projectile energy region included five main resonances allowing the determination of magnesium. The uncertainty of the cross-section determination was of the order of 7%. The applicability of the technique was tested using Mg-implanted AISI 321 steel samples. Depth resolution of 100 nm and detection limits of the order of 0.1 ppm were achieved for the determination of magnesium in steel samples using the 4805 keV resonance of the ²⁴Mg(α, p)²⁷ Al nuclear reaction. The shape and height of the magnesium depth-profile in the Mg-implanted steel samples were compared with corresponding values obtained by X-ray photoelectron spectroscopy. Received July 15, 1999. Revision March 30, 2000.     

Application of a CC Bond‐Forming Conjugate Addition Reaction in Asymmetric Dearomatization of β‐Naphthols

A C? C bond‐forming conjugate reaction was successfully applied to the enantioselective dearomatization of β‐naphthols. A C(sp2)? C(sp3) bond is formed by using propargylic ketones as reactive partners. Good to excellent Z/E ratios and ee values were obtained by employing an in situ generated magnesium catalyst. Further transformations of the Z‐configured C? C double bond in the products were achieved under mild reaction conditions. Moreover, the stereocontrolling element of this magnesium‐catalyzed dearomatization reaction was explored by computational chemistry.     

Synthesis and structure of anhydrous complexes of magnesium(II) with β-ketoesters of higher alcohols

Methods for the synthesis of anhydrous complexes of magnesium(II) with β-ketoesters of higher alcohols have been developed. A number of novel magnesium complexes of the general formula MgL₂ (where HL is hexyl-, dodecyl-, tert-butyl-, cyclohexyl-, bornyl- and 1-adamantyl acetoacetate), which are readily soluble in organic media, have been synthesized. It has been found by X-ray crystallography that bis(1-adamantyl acetoacetato)magnesium(II) has a trimeric structure. The structure of the complexes in solutions is discussed.