Coumarin-derivatized fluorescent <Emphasis Type="Italic">vic</Emphasis>-dioxime-type ligand and its complexes; the preparation,spectroscopy, and electrochemistry

A new vic-dioxime bearing coumarin functionality, N′¹,N′²-Dihydroxy-N ¹,N ²-bis(4-methyl-2-oxo-2H-chromen-7-yl)oxalimidamid (LH₂), N,N-bis-[4-methylcoumarinyl]-diamino glyoxime (LH₂), and its mono- and dinuclear complexes {copper^II, cobalt^II, nickel^II and uranyl^II} have been reported. The fluorescence excitation and emission spectra of LH₂ and its complexes with metal ions were examined. It was observed that fluorescence and excitation emission intensity of LH₂ was quenched depending on complex formation with metal ions. The characterizations of all newly synthesized compounds were made by elemental analysis, ¹H-n.m.r, i.r., u.v.–vis., and l.c-m.s./m.s. data. Electrochemical behaviour of the ligand involving oxime and coumarine moieties, and its complexes with Ni^II, Cu^II, Co^II and UO ₂ ^II were investigated by cyclic voltammetry. The comparison of the electrochemical behaviour of the ligand with its complexes enabled us to identify metal-, oxime- and coumarine-based signals.     

The synthesis and characterization of a new (<Emphasis Type="Italic">E,E</Emphasis>)-dioxime containing 13-membered dithiadiazamacrocyclic moieties and its mononuclear complexes

A new (E,E)-dioxime, (6Z,7Z)-15,16-dihydro-14H-dibenzo[b,h][1,10,4, 7]dithiadiazacyclotride-cine-6,7(5H,8H)-dionedioxime (H ₂ L) has been synthesized by reacting cyanogen-di-N-oxide (2) with 2,2′-[propane-1,3-diylbis(thio)]dianiline (1). Mononuclear complexes (4) and (5) of this ligand have been synthesized by reacting the vic-dioxime (H₂L) with NiCl₂ · 6H₂O and CoCl₂ · 6H₂O, respectively. The BF ₂ ⁺ capped Ni(II) and Co(III) complexes (6) and (7) of the dioxime have been synthesized from (4) and (5). The new compounds were characterized by a combination of elemental analysis, ¹H- and ¹³C-n.m.r, i.r. and m.s. spectral data.     

Nickel(II), palladium(II) and platinum(II) complexes of <Emphasis Type="Italic">N</Emphasis>-allyl-<Emphasis Type="Italic">N</Emphasis>′-pyrimidin-2-ylthiourea

Platinum(II), palladium(II) and nickel(II) complexes with N-allyl-N′-pyrimidin-2-ylthiourea were synthesized in 1:1 and 1:2 [metal:ligand] stoichiometric ratios and characterized by elemental analyses, molar conductivities, magnetic susceptibilities and by i.r., u.v.-vis., ¹H- and ¹³C-n.m.r. and mass spectra. The ¹H- and ¹³C- n.m.r. chemical shifts reveal coordination of one pyrimidine-N and sulphur atoms to Pt^II and Pd^II. The i.r. spectra indicate that the ligand behaves as a neutral monodentate towards Ni^II; coordinates via a pyrimidine-N and as a bidendate towards Pd^II and Pt^II coordinates via thione-S and a pyrimidine-N. The magnetic moments and electronic spectral data suggest a square-planar geometry for Pt^II and Pd^II complexes, a mixture of square-planar and tetrahedral geometries for the tetracoordinate Ni^II complex and octahedral for the six-coordinate one. The E.I. mass spectra of the complexes showed some isotope ion peaks of [M]⁺ and fragments containing metals; assignments of fragments containing metal ions were supported by the appearance of their peaks among isotope clusters.     

Syntheses of <Emphasis Type="Italic">tetrakis</Emphasis>(benzylisocyanide)<Emphasis Type="Italic">bis</Emphasis>(tri-<Emphasis Type="Italic">i</Emphasis>-propylphosphite) cobalt(III) tetrafluoroborate: comparison with trialkylphosphine–alkylisocyanide complexes of cobalt(III)

Tetrakis(benzylisocyanide)bis(tri-i-propylphosphite)cobalt(III) tetrafluoroborate, [Co(CNCH₂Ph)₄{P(OCHMe₂)₃}₂] (BF₄)₃, has been synthesized by ligand substitution of both [Co(CNCH₂Ph)₄{OAs(C₆H₄Me-p)₃}₂](BF₄)₃ and [Co(CNCH₂Ph)₄(OSbPh₃)₂](BF₄)₃. IR and electronic spectra, magnetic susceptibility, and cyclic voltammetric measurements are reported. The data are consistent with low-spin tetragonal coordination; i.e., trans-[Co(CNCH₂Ph)₄{P(OCHMe₂)₃}₂](BF₄)₃. Comparison is made with tetrakis(alkylisocyanide)bis(trialkylphosphine) cobalt(III) complexes.     

Synthesis of 4-[(1<Emphasis Type="Italic">R</Emphasis>,4<Emphasis Type="Italic">R</Emphasis>)-3-Oxo-<Emphasis Type="Italic">p</Emphasis>-menthan-2-ylidenemethyl]benzoic Acid and Its Esters

Carbonylation of (E)-2-(4-halobenzylidene)-p-menthan-3-ones, catalyzed by PdCl₂(PPh₃)₂, gave a distereometric mixure of 4-[(1R,4R)- and (1R,4S)-3-oxo-p-menthan-2-ylidenemethyl]benzoic acids, whose reaction with phenols gave 1R,4R diastereomers of the corresponding esters.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 659–664.Original Russian Text Copyright © 2005 by Drushlyak, Kutulya, Pivnenko, Vashchenko.     

Synthesis of new 1<Emphasis Type="Italic">H</Emphasis>-pyridazine derivatives <Emphasis Type="Italic">peri</Emphasis>-annelated with acenaphthene and acenaphthylene

The reaction of 6-acetyl-5-hydroxyacenaphthene with methylhydrazine afforded 1,3-dimethyl-1H-6,7-dihydroacenaphtho[5,6-de]pyridazine. Its dehydrogenation with chloranil gave 1,3-dimethyl-1H-acenaphtho[5,6-de]pyridazine, which is a heteroaromatic compound with an essentially new topology of the ρsystem. The reaction of 3-methyl-1H-6,7-dihydroacenaphtho[5,6-de]pyridazine with 3,5-di-tert-butyl-1,2-benzoquinone yielded a dimer containing the acenaphthene and acenaphthylene moieties of peri-annelated 1H-1,2-diazines connected in positions 1′ and 9.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 777–780, March, 2005.     

Contribution to the Protonation of a Calix[4]arene: DFT Calculated Structure of Protonated <Emphasis Type="Italic">p-tert</Emphasis>-Butylcalix[4]arenetetrakis(<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-diethylacetamide)

Summary. By using DFT calculations, the most probable structure of the p-tert-butylcalix[4]arenetetrakis(N,N-diethylacetamide) · H₃O⁺ complex species was derived. In this complex, the hydroxonium ion H₃O⁺ is predominantly bound by strong hydrogen bonds to three phenoxy oxygens of the ligand and partly to the remaining phenoxy oxygen atom by two somewhat weaker hydrogen bonds. Besides, the H₃O⁺ cation is also bound to two carbonyl oxygens of the mentioned ligand by further two weaker hydrogen bonds.     

Kinetic and mechanistic studies on the interaction between glycylglycine and <Emphasis Type="Italic">cis</Emphasis>-diaqua-<Emphasis Type="Italic">bis</Emphasis>-(bipyridine)-ruthenium(II) complex in aqueous medium

The kinetics of interaction between glycylglycine and cis-[Ru(bipy)₂(H₂O)₂]²⁺ have been studied spectrophotometrically as a function of [Ru(bipy)₂(H₂O) ₂ ²⁺ ], [diglycine] and temperature at a particular pH (4.8), where the substrate complex exists predominantly as the diaqua species and diglycine as the zwitter ion. The reaction has been found to proceed via two consecutive steps. The first step involves the ligand-assisted anation, while the second step involves chelation when the second aqua ligand is displaced. Rate constants have been evaluated and activation parameters calculated. The low enthalpy of activation and large negative values of entropy of activation indicate an associative mode of activation for both steps.     

Protonated Tetramethyl <Emphasis Type="Italic">p</Emphasis>-<Emphasis Type="Italic">tert</Emphasis>-Butylcalix[4]arene Tetraketone: NMR Evidence and Probable Structures

Summary. Both NMR spectra in nitrobenzene-d ₅ and high-precision quantum mechanical DFT calculations proved that tetramethyl p-tert-butylcalix[4]arene tetraketone binds hydroxonium cation H₃O⁺ quite strongly to form an equimolar complex. Three different structures of the resulting complex species were indicated by the NMR spectra and the DFT calculations.     

Preparation of a zwitterionic trichloroplatinum(II) complex with an alkylbipyridinum ligand and its reaction in dmso-<Emphasis Type="BoldItalic">d</Emphasis><Subscript>6</Subscript> solution

A zwitterionic trichloroplatinum(II) complex PtCl₃(4,4′-bpy-N-ⁿBu) (1) was prepared by an aqueous reaction of [4,4′-bpy-N-ⁿBu]Cl with K₂PtCl₄, and was characterized by ¹H-n.m.r. and IR spectroscopy as well as elemental analysis. Dissolving (1) into dmso-d ₆ at 25 °C yields a mixture of the complexes, cis-PtCl₂(4,4′-bpy-N-ⁿBu)(dmso-d ₆) (2-cis), trans-PtCl₂(4,4′-bpy-N-ⁿBu)(dmso-d ₆) (2-trans), [4,4′-bpy-N-ⁿBu]Cl and PtCl₂(dmso-d ₆)₂. Ratio of the products in the dmso-d ₆ solution changed depending on the temperature and the total concentration of the complexes. These compounds are in equilibrium via isomerization reaction between (2-cis) and (2-trans) and via displacement reaction of the alkylbipyridinium ligand of (2-cis) and (2-trans) with dmso-d ₆ to form [4,4′-bpy-N-ⁿBu]Cl and PtCl₂(dmso-d ₆)₂.     

A Kinetic and Mechanistic Study on Substitution of Aqua Ligands from <Emphasis Type="Italic">cis</Emphasis>-diaqua-<Emphasis Type="Italic">bis</Emphasis>-(bipyridyl)-ruthenium(II) Complex by Thiosemicarbazide in Aqueous Medium

The kinetics of the interaction of thiosemicarbazide with cis-[Ru(bipy)₂(H₂O)₂]²⁺ (bipy = α α′-bipyridyl) have been studied spectrophotometrically as a function of [Ru(bipy)₂(H₂O)₂²⁺], [bipyridyl] and temperature, at a particular pH (4.8), where the substrate complex exists predominantly as the diaqua species and thiosemicarbazide as the neutral ligand. The reaction proceeds via an outer sphere association complex formation, followed by two slow consecutive steps. The first is the conversion of the aforementioned complex into the inner sphere complex, and the second step involves the entrance of another thiosemicarbazide molecule in the coordination zone of Ru(II) whereby, in each step, an aqua ligand is replaced. The association equilibrium constant (K_E) for the outer sphere complex formation has been evaluated together with rate constants for the two subsequent steps. Activation parameters have been calculated for both steps using the Eyring equation (ΔH₁^# = 25.37±1.6 kJ mol⁻¹, ΔS₁^# = −215.48 ± 4.5 J K⁻¹ mol⁻¹, ΔH₂^# = 24.24 ± 1.1 kJ mol⁻¹, ΔS₂^# = −207.14 ± 3.0 J K⁻¹ mol⁻¹). The low enthalpy of activation and large negative value of entropy of activation indicate an associative mode of activation for both aqua ligand substitution processes. From the temperature dependence of K_E, the thermodynamic parameters calculated are: ΔH⁰ = 10.75±0.54 kJ mol⁻¹ and ΔS⁰ = 84.67 ± 1.75 J K⁻¹ mol⁻¹, which give a negative ΔG⁰ value at all temperatures studied, supporting the spontaneous formation of an outersphere association complex prior to the first step.     

Synthesis of 2-aryl-6-nitro-4-(<Emphasis Type="Italic">vic</Emphasis>-triazol-1-yl)-1<Emphasis Type="Italic">H</Emphasis>-indoles from <Emphasis Type="Italic">E</Emphasis>-2,4,6-trinitrostilbenes

A method is developed for the preparation of 4-(vic-triazol-1-yl)indoles that involves replacement of the ortho-NO₂ group in E-2,4,6-trinitrostilbenes by an azido group, condensation of E-2-azido-4,6-dinitrostilbenes with acetylacetone, replacement of the second ortho-NO₂ group in the resulting stilbenes by N₃, and subsequent thermolysis of the azide into the target indole. The reactions of E-2-azido-4,6-dinitrostilbenes with cyclohexane-1,3-dione gave E-2-amino-4,6-dinitrostilbenes, which can be used for selective transformation of the ortho-NO₂ group into an amino group in E-2,4,6-trinitrostilbenes. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1293–1296, May, 2005.     

Chemical Constituents of <Emphasis Type="Italic">Rhododendron lepidotum</Emphasis>

Two new coumarin glycosides, 7-O-β-D-glucopyranosyl-8-methoxybenzopyranone (1) and 7-hydroxy-8-O-β-glycosylbenzopyranone ((2), are reported along with the isolation of 7,8-dihydroxy coumarin (daphnetin) from Rhododendron lepidotum (aerial part).     

Cyclization of 2-Azido-3-(alkyl-<Emphasis Type="Italic">N</Emphasis>-nitrosoamino)-1,4-naphthoquinones to 1-Alkyl-1<Emphasis Type="Italic">H</Emphasis>-naphtho[2,3-<Emphasis Type="Italic">d</Emphasis>][1,2,3]triazole-4,9-dione 2-Oxides

Thermolysis of 2-azido-3-(alkyl-N-nitrosoamino)-1,4-naphthoquinones gives rise to compounds belonging to a new quinoid fused heterocyclic system, 1-alkyl-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione 2-oxides.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 926–927.Original Russian Text Copyright © 2005 by Radaeva, Dolgushina, Sakilidi, Gornostaev.     

<Emphasis Type="Italic">Raman</Emphasis> Spectroscopy and <Emphasis Type="Italic">Ab-Initio</Emphasis> Model Calculations on Ionic Liquids

Summary. A review of the recent developments in the study and understanding of room temperature ionic liquids are given. An intimate picture of how and why these liquids are not crystals at ambient conditions is attempted, based on evidence from crystallographical results combined with vibrational spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT-Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methylimidazolium ([C₄ mim][X]) salts. The rotational isomerism of the [C₄ mim]⁺ cation is described: the presence of anti and gauche conformers that has been elucidated in remarkable papers by Hamaguchi et al. Such presence of a conformational equilibrium seems to be a general feature of the room temperature liquids. Then the “localized structure features” that apparently exist in ionic liquids are described. It is hoped that the structural resolving power of Raman spectroscopy will be appreciated by the reader. It is of remarkable use on crystals of known different conformations and on the corresponding liquids, especially in combination with modern quantum mechanics calculations. It is hoped that these interdisciplinary methods will be applied to many more systems in the future. A few examples will be discussed.     

Synthesis from geraniol of (2<Emphasis Type="Italic">E</Emphasis>,6<Emphasis Type="Italic">E</Emphasis>,10<Emphasis Type="Italic">E</Emphasis>,14<Emphasis Type="Italic">E</Emphasis>)-16-hydroxygeranylgeraniol and some of its derivatives

Several α,ω-bifunctional derivatives of E,E,E-geranylgeraniol were prepared via convergent synthesis starting with geraniol (8), which was converted in three steps into the tetrahydropyranyl ether of 8-chlorogeraniol (9) and 8-hydroxygeranylphenylsulfone (10). Combination of synthons 9 and 10 with subsequent reductive removal of the phenylsulfonyl group produced the tetrahydropyranyl ether of ω-hydroxygeranylgeraniol (5), hydrolysis of which gave exclusively trans-ω-hydroxygeranylgeraniol (1). Derivatives 5–7 of geranylgeraniol were synthesized using standard methods. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 231–234, May–June, 2007.     

Synthesis and Stereochemistry of 1<Emphasis Type="Italic">H</Emphasis>,5<Emphasis Type="Italic">H</Emphasis>-Naphtho[1,8-<Emphasis Type="Italic">ef</Emphasis>][1,3]dithiocine 2-Oxides

3-Substituted 1H,5H-naphtho[1,8-ef][1,3]dithiocines (R = H, Me, Ph, t-Bu) were oxidized with m-chloroperoxybenzoic acid to the corresponding 2-oxides having trans configuration (R ≠ H). According to the ¹H and ¹³C NMR data (including NOESY experiments), the disubstituted compounds at room temperature exist in a boat conformation with equatorial orientation of the substituent on C³ and oxygen atom on S². The compound with no substituent on C³ gives rise to a mixture of boat conformers with axial and equatorial sulfoxide oxygen atoms at a ratio of 83:17.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005, pp. 1109–1112.Original Russian Text Copyright © 2005 by Kikilo, Khairutdinov, Shtyrlin, Klochkov, Klimovitskii.     

Insertion of ethyl diazoacetate into the platinum–carbon bond of Pt(diphosphine)(halide)(aryl) complexes. X-ray structure of the Pt{(2<Emphasis Type="BoldItalic">S</Emphasis>,4<Emphasis Type="BoldItalic">S</Emphasis>)-bdpp)}I(Ph) complex

Pt(diphosphine)X(aryl) complexes [diphosphine = 1,3-bis(diphenylphosphino)propane (dppp), 2,4-bis(diphenylphos phino)pentane (bdpp); aryl = phenyl, 2-thiophenyl; X = Cl, I] have been reacted with ethyl diazoacetate in chloroform. It has been revealed by in␣situ n.m.r. studies that the starting compounds insert the carbene, formed from ethyl diazoacetate, into the Pt–aryl group resulting in Pt(diphosphine)X{CH(aryl)COOC₂H₅}. Depending on the reaction conditions (reaction time, ratio of the reactants) and the ligands various side-reactions have been observed: (i) the formation of Pt(diphosphine)X₂ in chloroform, (ii) the insertion of the :CHCOOC₂H₅ fragment into the Pt–halide bond of the dihalogeno complexes Pt(diphosphine)X₂ resulting in the exclusive formation of Pt(diphosphine)X(CHXCOOC₂H₅). Diastereoselective insertion reactions have been observed in the presence of (S,S)-bdpp as diphosphine. The Pt{(S,S)-bdpp)}I(Ph) complex has been characterized by X-ray crystallography.     

<Emphasis Type="Italic">N,N′</Emphasis>-Bis(triethoxysilylmethyl)thiocarbamide and Poly[<Emphasis Type="Italic">N,N′</Emphasis>-bis(silsesquioxanylmethyl)thiocarbamide <Emphasis Type="Italic">S,S</Emphasis>-dioxide]

Condensation of (aminomethyl)triethoxysilane with thiocarbamide in the presence of catalytic amounts of ammonium sulfate was used to synthesize N,N-bis(triethoxysilylmethyl)thiocarbamide. The latter was brought into oxidative hydrolytic polycondensation with H₂O₂ to obtain poly[N,N′-bis(silsesquioxanylmethyl)thiocarbamide S, S-dioxide] whose properties were compared with the properties of poly[N,N′-bis(silsesquioxanylpropyl)thiocarbamide S,S-dioxide]. Both polymers in highly acidic media rather strongly absorb Ag(I), while at pH 7 they reduce most absorbed Ag⁺ to the metal. Their reaction with potassium permanganate involves reduction of Mn⁷⁺ to Mn⁴⁺. The first polymer is a less effective sorbent and redox agent than the second.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005, pp. 1154–1156.Original Russian Text Copyright © 2005 by Voronkov, Vlasova, Grigor’eva, Pozhidaev, Bol’shakova.     

Synthesis of substituted benz[<Emphasis Type="Italic">g</Emphasis>]indole-6,9-diones and benzo[<Emphasis Type="Italic">h</Emphasis>]quinoline-7,10-diones by heterocyclization of 6-alkynyl-5-amino-1,4-naphthoquinones

Substituted benz[g]indole-6,9-diones were synthesized by intramolecular cyclization of 6-alkynyl-5-amino-3-diethylamino-1,-4-naphthoquinones. A method was developed for the preparation of 2-aryl(or alkyl)-4,9-bis(dialkylamino)benzo[h]quinoline-7,10-diones, which involves the addition of a secondary amine to 6-acylethynyl-5-amino-3-diethylamino-1,-4-naphthoquinone followed by cyclization of the resulting adduct.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 412–418, February, 2005.