EPR spectroscopy in the analytical chemistry of technetium complexes

Electronic Paramagnetic Resonance (EPR) spectroscopy is used for studying paramagnetic Tc²⁺ and Tc⁶⁺ complexes, respectively. Results of liquid and frozen solution studies are discussed as well as those obtained from single-crystal experiments. Structure and bonding properties are derived from the spectral data.     

Fluorescent aluminum chelate complexes as modified precursors for nano-structured alumina

A series of new mononuclear heteroleptic derivatives of aluminum(III), {[(CH₃COCHCOCH₃)AlL] (1 and 4)}, {[(C₆H₅COCHCOC₆H₅)AlL] (2, 5, and 7)}, and {[(C₉H₆NO)AlL] (3 and 6)}, have been synthesized by reacting Al(OPrⁱ)₃ with tridentate Schiff base H₂L^x (H₂L¹ = C₁₃H₁₀BrNO₂; H₂L² = C₁₄H₁₃NO₃; H₂L³ = C₁₇H₁₃NO₂) and β-diketone/8-hydroxyquinoline (β-diketone = acetylacetone/dibenzoylmethane) in 1?:?1?:?1 stoichiometry using anhydrous benzene and ethanol. All the complexes were characterized by elemental analysis, FTIR, and NMR (¹H and ¹³C) spectral studies. Molecular structures obtained from single-crystal XRD of aqua 1 (1a) and DMSO coordinated 2 (2a) authenticate their existence. Further, nanostructured α-alumina was synthesized from 1 by well-established sol–gel method and was characterized by powder XRD, TEM, and EDX analyses.     

EPR spectroscopy as a probe of metal centres in biological systems

Molecular paramagnetism pervades the bioinorganic chemistry of V, Mn, Fe, Co, Ni, Cu, Mo, W, and of a number of non-biological transition elements. To date we can look back at half a century of fruitful EPR studies on metalloproteins, and against this background evaluate the significance of modern EPR spectroscopy from the perspective of a biochemist, making a distinction between conventional continuous wave X-band spectroscopy as a reliable work horse with broad, established applicability even on crude preparations, vs. a diffuse set of "advanced EPR" technologies whose practical application typically calls for narrowly focused research hypotheses and very high quality samples. The type of knowledge on metalloproteins that is readily obtainable with EPR spectroscopy, is explained with illustrative examples, as is the relation between experimental complexity and the spin value of the system.     

Substitution kinetics of chelate complexes as studied by isotopic exchange

The fact that isotopic exchange reactions take place at chemical equilibirum makes this type of reaction useful for kinetic studies. In the case of chelate complexes [M(chel)_n] isotopic exchange reactions can be classified as metal exchange reactions. [M(chel)_n]+^*M⇆[^*M(chel)_n]+M and ligand exchange reactions [M(chel)_n]+^*chel⇆[M(chel)_n−1 ^*chel]+chel The literature on type (a) and type (b) reactions of mainly transition metal complexes is reviewed with respect to the kinetic information obtained. The value and the limitations of isotopic exchange studies as a kinetic technique are discussed.     

Ir spectroscopy of 2,3-polymethylene-3,4-dihydroquinazolines and their complexes

We have investigated the IR spectra in the region of stretching vibration of N⁺–H and OH groups of the hydrochlorides of 2,3-trimethylene-3,4-dihydroquinazoline (deoxypeganine, DOP), 2,3-tetramethylene-3,4-dihydroquinazoline (tetrazoline), and 2,3-pentamethylene-3,4-dihydroquinazoline (pentazoline) and peganol and peganine and the corresponding complexes with ZnCl₂, CoCl₂, and MnCl₂. The appearance of two additional absorption bands in the 3100–3300 cm^–1 region in the complexes investigated as compared with the corresponding hydrochlorides witnesses the formation of interionic hydrogen bonds between the quinazoline cation and the (MeCl₄)^2– anion.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 40 64 75. Translated from Khimiya Prirodnykh Soedinenii, No. 6., pp. 854–857, November–December, 1997.     

Boron trihalide-methyl sulfide complexes as convenient reagents for dealkylation of aryl ethers

High yield dealkylation of several aryl methyl ethers was observed upon exposure of these compounds to an excess of the boron trihalide-methyl sulfide complexes.     

Study of a system for introducing metal chelate complexes in AAS

Summary The possibility of extending the sampling of volatile phases in AAS by use of metal beta-diketonates is considered. An electrically heated system was designed in which the chelate was injected, volatilized and then carried by a nitrogen stream to a silica tube, which was heated with an air-acetylene flame. The method was investigated for Cr, Zn and Mn using acetylacetone as chelating agent. The introduction of volatile chelates gives an increase in sensitivity with respect to the nebulization and atomization of solutions in the flame. This sampling system is limited to metallic chelates which are thermally stable and sufficiently volatile. The partial decomposition, which Zn acetyl-acetonate and, particularly Mn acetylacetonate undergo, causes a reduction in the sensitivity and precision of the determination.

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Untersuchung eines Probeeingabesystems für Metallchelatkomplexe in der AASEinfluß der Chelatstabilität

     

A convenient method for the synthesis of 2,3-dioxo-1,2,3,4-tetrahydroquinoxalines

A method for the synthesis of substituted 2,3-dioxo-1,2,3,4-tetrahydroquinoxalines by the reduction of substituted (o-nitrophenyl)glycines with subsequent oxidation of the 2-oxo-1,2,3,4-tetrahydroquinoxaline products has been developed. When tin(II) chloride was used as the reducing agent a chlorine atom was introduced ortho to the NHC(O) fragment of the heterocycle. __________ Translated from Khimiya Geterotsikicheskikh Soedinenii, No. 8, 1206–1210, August, 2006.     

Fourier transform infrared spectroscopy as a tool for the study of rare earths carbohydrates complexes

FT-IR spectra of the mixtures of praseodymium chloride and glucose in glassy state were investigated. From the changes of relative intensity and shifts of the characteristic frequency of glucose and water, it is concluded that the coordinated water molecules of the praseodymium ions are partially substituted by glucose through O-H groups which coordinated with praseodymium ions to form chelate ions.     

Tribochemically active chelate complexes of salicylideneimines

N-Alkylsalicylideneimines and their complexes with 3d metals were obtained by chemical (from metal salts) and electrochemical methods (from metals in the zero oxidation state). The compounds obtained were characterized by IR and ¹H NMR spectroscopy and X-ray diffraction analysis. According to crystallographic data, nickel bis(chelate) exists in the trans-planar configuration. A friction test revealed that the tribotechnical characteristics of lubricating formulations are substantially enhanced in the presence of N-alkylsalicylideneiminates.     

Combination of low-temperature photolysis and ESR spectroscopy as a method for investigating nonparamagnetic complexes

The possibility of the use of ESR for investigating coordination compounds formed by ions of transition metals having no d electrons has been demonstrated on the basis of an analysis of the data obtained on the low-temperature photolysis of labile complexes of titanium(IV), vanadium(V), and molybdenum(VI). Under the proposed procedure, the d complex is converted into a d¹ complex by means of photochemical reduction under conditions which are favorable to the maintenance of the coordination sphere unchanged, its ESR spectrum is recorded, and the parameters obtained are used to characterize the composition, structure, symmetry, and degree of aggregation of the original compound in the solution. The use of this procedure is restricted to the investigation of systems in which photochemical redox conversions are realized according to an outer-sphere mechanism; however, it may also be useful in the interpretation of the results of the photolysis of compounds which undergo inner-sphere conversions.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 197–203, March–April, 1989.     

EPR spectra from "EPR-silent" species: high-frequency and high-field EPR spectroscopy of pseudotetrahedral complexes of nickel(II)

High-frequency and high-field electron paramagnetic resonance (HFEPR) spectroscopy (using frequencies of approximately 90-550 GHz and fields up to approximately 15 T) has been used to probe the non-Kramers, S = 1, Ni(2+) ion in a series of pseudotetrahedral complexes of general formula NiL(2)X(2), where L = PPh(3) (Ph = phenyl) and X = Cl, Br, and I. Analysis based on full-matrix solutions to the spin Hamiltonian for an S = 1 system gave zero-field splitting parameters: D = +13.20(5) cm(-1), /E/ = 1.85(5) cm(-1), g(x) = g(y) = g(z) = 2.20(5) for Ni(PPh(3))(2)Cl(2). These values are in good agreement with those obtained by powder magnetic susceptibility and field-dependent magnetization measurements and with earlier, single-crystal magnetic susceptibility measurements. For Ni(PPh(3))(2)Br(2), HFEPR suggested /D/ = 4.5(5) cm(-1), /E/ = 1.5(5) cm(-1), g(x) = g(y) = 2.2(1), and g(z) = 2.0(1), which are in agreement with concurrent magnetic measurements, but do not agree with previous single-crystal work. The previous studies were performed on a minor crystal form, while the present study was performed on the major form, and apparently the electronic parameters differ greatly between the two. HFEPR of Ni(PPh(3))(2)I(2) was unsuccessful; however, magnetic susceptibility measurements indicated /D/ = 27.9(1) cm(-1), /E/ = 4.7(1), g(x) = 1.95(5), g(y) = 2.00(5), and g(z) = 2.11(5). This magnitude of the zero-field splitting ( approximately 840 GHz) is too large for successful detection of resonances, even for current HFEPR spectrometers. The electronic structure of these complexes is discussed in terms of their molecular structure and previous electronic absorption spectroscopic studies. This analysis, which involved fitting of experimental data to ligand-field parameters, shows that the halo ligands act as strong pi-donors, while the triphenylphosphane ligands are pi-acceptors.     

No-D NMR spectroscopy as a convenient method for titering organolithium (RLi), RMgX, and LDA solutions

[reaction: see text] The concentration of organolithium, organomagnesium halide, and lithium diisopropylamide solutions can be reliably determined using No-D NMR spectroscopy by integration against the added internal standard 1,5-cyclooctadiene (COD) (or cyclooctene). In addition, common impurities and degradation products can be assessed.     

Quantum chemical aspects of the chelate effect in complexes

A typical “chelate” effect is demonstrated by means of all-electron ab initio LCGO SCF calculations on the [Li(HCONH₂)₂]⁺ complex in different geometrical arrangements. Energetic factors and the electronic structure of the complexes are discussed, showing the chelate effect to be connected with striking changes in bonding, density distribution and electronic energy.     

On the application of homonuclear NOE difference spectroscopy as a convenient tool for configurational assignment of compounds with a C=N bond

Summary The applicability of homonuclear NOE difference spectroscopy for configurational assignment of compounds characterized by a -CH=N-R substructure is evaluated employing phenylhydrazones, benzenesulfonylhydrazones, (thio)semicarbazones, and oxime ethers derived from heteroaromatic carbaldehydes.Dedicated to Prof. Dr. F. Sauter with cordial wishes on the occasion of his 60th anniversary