New cobalt and iron pivalate complexes with 2,2′:6′,2″-terpyridine: synthesis, structure, and magnetic properties

The mononuclear complexes (η³-terpy)M(Piv)²·MeCN (M = Fe ⁱⁱ (3) and Co ⁱⁱ (4), and Piv is the pivalate anion) were synthesized by the reactions of polymeric iron(ii) and cobalt(ii) pivalates with 2,2′:6′,2″-terpyridine (terpy). The oxidation of compound 3 affords the pentanuclear heterospin iron(ii,iii) complex (η³-terpy)Fe₅(μ₄-O)(μ₃-OH)(μ-OH)₂(μ-Piv)₇(η¹-Piv)₂ (5). All compounds were characterized by X-ray diffraction. Dedicated to the 90th anniversary of the L. Ya. Karpov Institute of Physical Chemistry. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1186–1190, June, 2008.     

Oxidation with manganate solutions

Summary The reaction between Tl⁺ solutions and manganate is sluggish. In the titration of Tl⁺ with manganate solution the end points are always attained earlier than the theoretical. When the reaction is accelerated by NaCl and heating to 45–50° C the end points were found to be concordant with the theoretical values. Titration of manganate with Tl⁺ solutions gives accurate results in presence of telluric acid but not in its absence. It is also possible to determine Tl⁺ by oxidation with an excess of K₂MnO₄ using arsenite as a back titrant for excess oxidant.Part III: Issa, I. M., and M. G. E. Allam: Z. analyt. Chem. 175, 103 (1960).     

Untersuchungen über die Biosynthese der Cyclite, 22. Mitt.: Cyclite inChlorella fusca

Zusammenfassung Das Vorkommen von Cycliten inChlorella fusca wurde mit Hilfe der Methode der Photoassimilation in einer Atmosphäre von¹⁴CO₂ untersucht. Außer dem bereits als Bestandteil dieser Algenart bekanntenmyo-Inosit konnten auch andere Cyclite, nämlichd-chiro-Inosit, Mytilit, Laminit undl-Leucanthemit nachgewiesen werden. Einbauversuche mit markierten Vorstufen ergaben, daßmyo-Inosit höchstwahrscheinlich auf dem schon in vielen Organismen nachgewiesenen Weg ausd-Glucose entsteht undd-chiro-Inosit das Produkt einer direkten Epimerisierung vonmyo-Inosit ist. Hingegen besteht keine biogenetische Beziehung zwischenmyo-Inosit und den beiden C-Methylinositen Mytilit und Laminit; die Methylgruppe vonl-Methionin wird nicht in diese beiden Verbindungen eingebaut.

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Studies on the biosynthesis of the cyclitols, XXII: Cyclites in chlorella fusca

The occurrence of cyclitols inChlorella fusca has been studied, using the method of photoassimilation in an atmosphere of¹⁴CO₂. Besidesmyo-inositol which is known to be a constituent of this algal species, other cyclitols were detected, namelyd-chiro-inositol, mytilitol, laminitol, andl-leucanthemitol. Incorporation experiments with labelled precursors make it most probable thatmyo-inositol is formed fromd-glucose through a pathway already established in many organisms, whereasd-chiro-inositol is the product of a direct epimerization ofmyo-inositol. No biogenetic relation exists betweenmyo-inositol and the two C-methylinositols; the methyl group ofl-methionine is not incorporated into these compounds.

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21. Mitt.:E. Molinari undO. Hoffmann-Ostenhof,Z. physiol. Chem.349, 1797 (1968).     

Oxidations with potassium permanganate in the presence of fluoride

Summary Trivalent chromium and quadrivalent vanadium can be determined with fair accuracy by a method consisting in mixing either with an excess of KMnO₄ in the presence of 0.3 to 1.8 M alkali hydroxide. After leaving the mixture for 5 min, the solution is acidified with sulphuric acid and mixed with 50 to 75 ml of 2% NaF solution. An excess of monovalent mercury Hg₂ ²⁺ solution is then added, the solution heated to 40° C and then titrated with KMnO₄ solution in the presence of Cu²⁺ ions to conceal the pink manganic fluoride colour.Part II: Issa, I. M., and M. Hamdy: Z. analyt. Chem. 172, 162 (1960).     

Determination of Binding Constants of Polyethylene Glycol Vancomycin Derivatives to Peptide Ligands Using Affinity Capillary Electrophoresis

Vancomycin (Van) from Streptomyces orientalis has been derivatized with polyethylene glycol [PEG; PEG-550 (1), 750 (2), 1,100 (3), 2,000 (4), 5,000 (5), and 8,000 (6) g mol⁻¹] at the N-terminus of the glycopeptide backbone and their binding to d-Ala-d-Ala terminus peptides assessed using affinity capillary electrophoresis (ACE). Utilizing ACE, a plug of Van-PEG and non-interacting standards are injected and electrophoresed. Analysis of the change in the relative migration time ratio of the Van-PEG species, relative to the non-interacting standards, as a function of the concentration of peptide, yields a value for the binding constant (K _b). Values of K _b for N-acetyl-d-Ala-d-Ala, 7 to the Van-PEG derivatives are weaker than those for N _α,N _ε-diacetyl-Lys-d-Ala-d-Ala, 8 (for example, values of K _b for 7-1 and 8-1 are 1.8 and 47.7 × 10³ M⁻¹, respectively). These results demonstrate that derivatization of Van with PEG has little effect on the affinity of d-Ala-d-Ala peptide ligands to it. The findings further prove the versatility of ACE and its ability to estimate binding parameters of ligands to antibiotics.     

Computer estimation of dissociation constants. Part IV. Precision and accuracy of potentiometric determinations

The protonation constants logK _Hj of the acidH _J are determined by regression analysis of potentiometric titration data whencommon parameters (logK _Hj,j = 1,...,J) andgroup parameters (E ⁰,L ₀,H _T ) are refined. Two kinds of systematic error have been investigated: the error from an uncertainty of group parameters and the error from a computational strategy of the minimization algorithm used. An analysis of variance of logK _Hj matrix was made for 6 reproduced titrations and 7 computational strategies of 6 various regression programs. It was concluded that the influence of the program used is negligible. From two ways of calibration of the glass electrode cell,the internal calibration (performed during titration) was slightly more accurate thanthe external calibration (done separately). Of programs tested, the ESAB and ACBA are most powerful because they permit refinement of group parameters and internal calibration. D-tartaric acid was chosen as model substance.Previous Part III.: Iraqi J. Sci.1981,22, 67.     

Untersuchungen über die Biosynthese der Cyclite, 17. Mitt.: Bildung vond-bornesit und Dambonit inNerium oleander

Zusammenfassung Dambonit (1,3-Di-O-methyl-myo-inosit) entsteht inNerium oleander, wie durch Einbauversuche mit radioaktiv markiertemmyo-Inosit undd-Bornesit sowie durch Bestimmung der Zeitabhängigkeit der Bildung der Cyclite bei Assimilation von¹⁴CO₂ nachgewiesen wurde, ausmyo-Inosit überd-Bornesit als Zwischenprodukt. Neben Dambonit finden sich in der Cyclitfraktion vonN. oleander auchd-Bornesit,myo-Inosit sowiel-Leucanthemit.myo-Inosit unterliegt in der Pflanze-besonders im Winter-einem sehr intensiven Stoffwechsel, der zu nichtzyklischen Verbindungen führt.

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InNerium oleander dambonitol (1,3-Di-O-methyl-myo-inositol) is formed frommyo-inositol withd-bornesitol as intermediate, as could be shown with the help of incorporation experiments with radioactively labelledmyo-inositol andd-bornesitol and also by the determination of the time dependence of the formation of the cyclitols from¹⁴CO₂ in photoassimilation experiments. Besides dambonitol the cyclitol fraction ofN. oleander contains alsod-bornesitol,myo-inositol andl-leucanthemitol. Especially in wintermyo-inositol undergoes a very active catabolism in the plant which leads to the formation of non-cyclic compounds.

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H. Kindl undO. Hoffmann-Ostenhof, Mh. Chem.97, 1771 (1966).     

Oxidations with potassium permanganate in the presence of fluoride

Summary Quadrivalent selenium can be determined with fair accuracy by mixing with an excess of KMnO₄ in the presence of 25–75 ml of 2% NaF solution and 4–7 ml of 9 N sulfuric acid. After leaving the reaction mixture for 10–30 minutes the excess KMnO₄ is estimated by one of the following procedures: A) Titration of the excess KMnO₄ with monovalent mercury, B) Adding an excess of Hg₂ ²⁺ solution to react with the excess KMnO₄ followed by titrating the excess mercurous with KMnO₄ solution.Part I: Issa, I. M., and M. Hamdy, Z. analyt. Chem. 172, 94 (1980).     

Oxidations with potassium permanganate in the presence of fluoride

Summary The titration of ferrous iron in presence of fluoride ions in acid medium gives fleeting end points and erroneous results. A method is deviced to overcome this difficulty by oxidising the ferrous with an excess of KMnO₄ in alkaline medium. After mixing the reactants the excess of KMnO₄ is reduced by an excess of Hg₂ ²⁺ ions in presence of H₂SO₄ and fluoride. The remaining mercurous is then titrated with standard KMnO₄ solution.Part III: Issa, I. M., and M. Hamdy: Z. analyt. Chem. 174, 418 (1960).     

Dimericd- anddl-dysprosium(iii) tartrates: paramagnetic birefringence,molecular mechanics,stereoselectivity

The molar constants of paramagnetic birefringence (PBR) for the dimeric dysprosium(iii)d- anddl-tartrates, Dy₂(d-Tart)(l-Tart)^2– (1) and Dy₂(d-Tart)₂ ^2– (2) have been determined by means of pH-metric and PBR measurements. The simulation of the structure of the ligand and solvate environment has been carried out using the method of molecular mechanics (Dashevsky-Plyamovaty model, the MIND program). In addition to the four oxygen atoms from the ligand, each Dy^III ion coordinates four molecules of water and a Na⁺ ion.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1029–1032, June, 1994.     

One Novel Cu(II)–Amino Acid Schiff Base Complex Derived from Salicylaldehyde and L-Serine: Identification of Unusual Monodentate 4,4′-Bipyridine

One novel copper(II) complex [Cu(L)(4,4′-bipy)](ClO₄) (1), (where L: tridentate Schiff base derived from salicylaldehyde and L-serine) has been synthesised and characterised by spectroscopic and electrochemical studies. The single-crystal structure of the complex was determined. The crystal structure features the presence of [Cu(L)(4,4′-bipy)]⁺ cations and ClO₄⁻ anions aggregated by hydrogen bonding. Here, 4,4′-bipyridine functions as a monodentate ligand, which appears to be an unusual phenomenon.     

Inclusion compounds of the copper(<Emphasis Type="SmallCaps">ii</Emphasis>) and zinc(<Emphasis Type="SmallCaps">ii</Emphasis>) complexes with cyclam in cucurbit[8]uril: synthesis and structure

Inclusion compounds of the macrocyclic cavitand cucurbit[8]uril (CB[8], C₄₈H₄₈N₃₂O₁₆) with the copper(ii) and zinc(ii) complexes with the tetraazamacrocyclic ligand cyclam, {[Cu(cyclam)(H₂O)₂]@CB[8]}Cl₂·18H₂O (1) and {[Zn(cyclam)]@CB[8]}Cl₂·13H₂O (2), were synthesized. The compounds were characterized by X-ray diffraction analysis, electrospray mass spectrometry, IR spectroscopy, and elemental analysis. The ¹H and ¹³C NMR method revealed only one trans-isomer of the zinc(ii) complex with cyclam in an aqueous solution of inclusion compound 2.     

Solochrome Black P. V. as a new reagent in chelatometry

Summary Solochrome Black P. V. with its distinct acid-base properties has proved to be a suitable reagent for the spectrophotometric microdetermination of magnesium either alone or in the presence of zinc, calcium, cobalt, or copper. Interference due to many cations is simply eliminated. Spectrophotometric titration of magnesium with EDTA is investigated. Sensitivity of the method allows determining of 0.05 to 3 ppm Mg with reasonable accuracy.

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Zusammenfassung Solochromschwarz P. V., das als Säure-Base-Indicator verwendet werden kann, ist auch ein geeignetes Reagens zur spektrophotometrischen Mikrobestimmung von Magnesium. Zink, Calcium, Kobalt, Kupfer und andere Kationen können in einfacher Weise maskiert werden. Die spektrophotometrische Titration des Magnesiums mit ÄDTA-Lösung wird ebenfalls untersucht. 0,05–3 ppm Mg können mit guter Genauigkeit bestimmt werden.

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Part II:Khalifa, H., and M. M.Khater: Z. analyt. Chem.183, 241 (1961).     

IR and <Superscript>31</Superscript>P NMR spectroscopic study of complexation of carbamoyl methyl phosphinates with U<Superscript>VI</Superscript> and Th<Superscript>IV</Superscript> in nitric acid solutions

The composition of complexes formed upon the extraction of U^VI and Th^IV nitrates with O-n-nonyl(N,N-dibutylcarbamoylmethyl) methyl phosphinate (L) from solutions of nitric acid without additional solvent was determined by ³¹P NMR spectroscopy. The structures of the complexes formed were studied by IR spectroscopy. Uranium(VI) is extracted from 3 and 5 M solutions of HNO₃ as the [UO₂(L)₂(NO₃)₂] complex, while thorium(IV) is extracted from 5 M HNO₃ as the [Th(L)₃(NO₃)₃]⁺·NO ₃ ⁻ complex. In both cases, ligand L has bidentate coordination. Ligand L contacts with 3 and 5 M nitric acid to form adducts L·HNO₃ and L· (HNO₃)₂, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2460–2464, November, 2005.     

Coordination chemistry of 2,6-bis(diphenylphosphorylmethyl)-4-methylphenol

The trifunctional ligand, 2,6-bis(diphenylphosphorylmethyl)-4-methylphenol (L ₂), forms complexes with cerium(III) nitrate having a ligand to metal ratio of 1: 1, 2: 1, and 3: 1. The structures of these complexes in the solid state and in solution were studied by X-ray diffraction, IR and NMR (¹H and ³¹P) spectroscopy, and conformational analysis (molecular mechanics). The 2: 1 complexes of L ₂ with lanthanum(III) and neodymium(III) nitrates were synthesized and characterized. In all complexes, the neutral ligand is coordinated through both phosphoryl oxygen atoms. The hydroxy oxygen atom is coordinated only in some complexes, and the hydrogen atom of the hydroxy group is involved in hydrogen bonding. The compositions and structures of the resulting complexes depend on the method of synthesis and the nature of solvent. The ligand was found to undergo easy inner-sphere oxidation. The structure of one of the transformation products was established by X-ray diffraction. Unlike the coordinated ligand, the free ligand is very stable to oxidation. Dedicated to Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2440–2454, November, 2005.     

1H,13C NMR spectral data for α-, β-, and γ-lewisites and identification ofcis,trans, trans-γ-lewisite as a new isomer

The¹H and¹³C NMR spectral parameters of α-, β-, and y-lewisites1–5 were obtained and a new isomer,cis,trans,trans-γ-lewisite5, was isolated and identified on the basis of chemical shifts, relative intensities of the signals, and the intra-chain (³ J _hh ,³ J _ch ) and interchain (³ J _casch ) coupling constants. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1833–1835, October, 1993.     

Replacement of Fe atoms by Ru in a carbidocarbonyl cluster [Fe<Subscript>6</Subscript>C(CO)<Subscript>16</Subscript>]<Superscript>2−</Superscript>. Structures of reaction products

The reaction of the carbidocarbonyl cluster [Fe₆C(CO)₁₆]²⁻ with ruthenium(IV) hydroxochloride Ru(OH)Cl₃ was studied. At 90–100 °C, the reaction gave products of replacement of Fe atoms by Ru in the [Fe₆C(CO)₁₆]²⁻ cluster along with degradation products. Treatment of the replacement products with FeCl₃ afforded the [Fe_2.96Ru_3.04C(CO)₁₇] compound (1), which was characterized by X-ray diffraction analysis. The crystals of cluster 1 are composed of two types of octahedral molecules (1a and 1b) in a ratio of 2 : 1. Molecules 1a are in general positions, and molecules 1b are located on twofold axes. In both molecules, the Fe and Ru atoms are disordered over four of six positions. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1761–1766, August, 2005.     

Liquid-crystalline CuII and PdII complexes with nonmesogenic ferrocene-containing β-aminovinyl ketone

New liquid-crystalline heteropolynuclear complexes L₂M (M=Cu²⁺ (2a), Pd²⁺ (2b)) were synthesized by the reactions of C₅H₅FeC₅H₄−C₆H₄NH−C₂H₂−(CO)−C₆H₄OC₁₂H₂₅ (1, LH) with copper(ii) and palladium(ii) acetates. Compound2b was found to possess monotropic nematic and smectic phases;2a exhibits the monotropic nematic phase and a phenomenon of “double melting”. The compositions and structures of compounds1 and2a,b were established by elemental analysis,¹H and¹³C NMR, ESR, and IR spectroscopy. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 381–383, February, 1999.     

The chemiluminescence of dispiro(1,2-dioxetane-diadamantane) sorbed on silipore activated by a phenanthroline complex of Eu(iii)

The thermal decomposition of dispiro(1,2-dioxetane-diadamantane) (1) sorbed on silipore containing EuCl₃ ando-phenanthroline was investigated. The observed chemiluminescence is caused by radiative deactivation of EU^*(iii) formed according to an energy transfer mechanism. Chemiluminescence decay in the course of the decomposition of1 is exponential with the rate constantk. The activation parameters of the decomposition of1 sorbed on silipore were determined from the temperature dependence ofk. These parameters are independent of the Eu(iii) content. A kinetic compensating effect was found: the dependence of logA onE _a as a function of the content of1. The mechanism of the compensating effect is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 447–451, March, 1995.     

Reactions of germanium(II), tin(II), and antimony(III) chlorides with acenaphthene-1,2-diimines

Reactions of diimines dtb-BIAN and dph-BIAN with GeCl₂ afford germanium(II) complexes with radical-anionic ligands, (dtb-BIAN)GeCl (5) and (dph-BIAN)GeCl (6a), respectively, where dtb-BIAN is 1,2-bis[(2,5-di-tert-butylphenyl)imino]acenaphthene and dph-BIAN is 1,2-bis[(2-biphenyl)imino]acenaphthene. The latter reaction gives 6a along with [(dph-BIAN)GeCl]⁺[GeCl₃]⁻ (6b). The reactions of tin(II) and antimony(III) chlorides with dtb-BIAN and dpp-BIAN produce complexes of these halides with neutral coordinated diimines, viz., (dtb-BIAN)SnCl₂ (7) and (dpp-BIAN)SbCl₃ (8) (dpp-BIAN is 1,2-bis[(2,6-di-isopropylphenyl)imino]acenaphthene). Paramagnetic complexes 5 and 6a were studied by ESR spectroscopy. Diamagnetic compounds 7 and 8 were characterized by ¹H NMR spectroscopy. The structures of complexes 5, 6a,b, 7, 8, and (dpp-BIAN)Ge (9) were established by X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 71–80, January, 2006.