Synthesis and spectral properties of some bis-substituted formazans

Novel, 1,4-bis-[3,3'-phenyl-5,5'-(o-carboxyphenyl)-formaz-1-yl]-benzene-o-sulphonic acid and its derivatives contained OH group at the o-, m-, p-positions of the 3-phenyl ring were synthesized. The structures of the formazans were confirmed by elemental analyses, GC-mass, IR, (1)H NMR, UV-vis spectra. Their absorption properties were investigated. It was seen that lambda(max) values shifted towards shorter wave lengths by 130nm in CSPF relative to 1,3,5-triphenylformazan (TPF) due to the fact that the structure of CSPF contained electron withdrawing COOH and SO(3)H groups (hypsochromic effect). With binding of OH group to 3-phenyl ring of CSPF, it was observed a small bathochromic effect in accordance to the electron donating effect of OH group.     

Cationic polyisoprene: Synthesis,structure, and some properties

Russian Journal of Applied Chemistry - The effect of the catalyst composition and temperature on the cationic polymerization of isoprene in the presence of the catalytic system...     

Synthesis,structure and some properties of a new polyalcohol

A new polyalcohol (CH₂CH₂CH(OH))_n was synthesized from 1:1 ethylene/carbon monoxide alternating copolymer (polyketone) by reduction with sodium borohydride. Some structural and chemical properties are described.     

Synthesis, structure investigation, spectral characteristics and biological activities of some novel azodyes

Four novel azo compounds were synthesized; o-phenylazo- (C(14)H(13)N(3)O(2)) (I), p-bromo-o-phenylazo- (C(14)H(13)BrN(3)O(2)) (II), p-methoxy-o-phenaylazo- (C(15)H(16)N(3)O(3)) (III) and p-nitro-o-phenylazo-p-acetamidophenol (C(14)H(13)N(4)O(4)) (IV). These compounds were carefully investigated using elemental analyses, UV-vis, FT-IR, (1)H NMR and mass spectra. Also, the effects of p-substituents such as bromo, methoxy and nitro groups on the mass fragmentation pathways of these dyes were studied using Hammet's effects. This research aimed chiefly to threw lights on the structures-stability relationship of four novel newly prepared azo derivatives of p-acetoamidophenol. The data obtained referred to the variation of mass fragmentation pathways with the variation of p-substituent of these dyes which can be used in industry for various dyeing purposes. This variation is also correlated and verified by molecular orbital calculations which were done on ionic forms of these dyes using semi empirical PM3 program. The biological activities of these dyes were also investigated and its structure relationship was correlated.     

Synthesis, crystal structure and some physical properties of RuZn3

The crystal structure, phase relations and some physical properties of the binary zinc-rich phase RuZn3 are reported. The title compound is accessible via high-temperature reaction from the elements in the appropriate substance amount ratio. Its crystal structure was determined from a Rietveld profile fit to an X-ray diffractogram of pristine RuZn3 and confirmed by single-crystal X-ray structure analysis. The title compound adopts a tetragonal Al3Zr-type structure corresponding to an A2B2 anti-phase domain structure of the cubic AuCu3-type: a=376.82(3) pm, c=1554.78(13) pm, I4/mmm, Z=4, R(F)(all data)=0.0197, 153 unique reflections, 12 variables. The structure is discussed in the light of the Hume-Rothery concept. RuZn3 melts at 1373(2) K, is a moderate metallic conductor (rho(293 K)=6.2 mOmega cm) and exhibits basically temperature-independent paramagnetic properties. It coexists with Ru1-xZnx and RuZn6.     

Synthesis,structure and electrochemical properties of some thiosemicarbazone complexes of iridium

Reaction of thiosemicarbazones of salicylaldehyde and 2-hydroxyacetophenone (H₂L¹ and H₂L²) with [Ir(PPh₃)₃Cl] affords complexes of type [Ir(PPh₃)₂(L)(H)] (L = L¹ or L²) in ethanol. A similar reaction carried out in toluene affords the [Ir(PPh₃)₂(L)(H)] complexes along with complexes of type [Ir(PPh₃)₂(L)Cl], where a chloride is coordinated to iridium instead of the hydride. The structure of the [Ir(PPh₃)₂(L²)(H)] and [Ir(PPh₃)₂(L²)Cl] complexes has been determined by X-ray crystallography. Crystal data for [Ir(PPh₃)₂(L²)(H)]: space group, P2₁/c; crystal system, monoclinic; a=12.110(2) Å, b=17.983(4) Å, c=18.437(4) Å, β=103.42(3)°, Z=4; R ₁=0.0591, wR ₂=0.1107. Crystal data for [Ir(PPh₃)₂(L²)Cl]: space group, P2₁/c; crystal system, monoclinic; a=17.9374(11) Å, b=19.2570(10) Å, c=24.9135(16) Å, β=108.145(5)°, Z=4; R ₁=0.0463, wR ₂=0.0901. In all the complexes the thiosemicarbazones are coordinated to the metal center as dianionic tridentate O, N, S-donors and the two triphenylphosphines are trans. The complexes are diamagnetic (low-spin d? ⁶, S=0) and show intense MLCT transitions in the visible region. Cyclic voltammetry on all the [Ir(PPh₃)₂(L)(H)] and [Ir(PPh₃)₂(L)Cl] complexes shows a quasi-reversible Ir(III)–Ir(IV) oxidation within 0.55–0.78 V vs. SCE followed by an irreversible oxidation of the thiosemicarbazone within 0.91–1.27 V vs. SCE. An irreversible reduction of the thiosemicarbazone is also observed within ?1.10 to ?1.23 V vs. SCE.     

o-Cyclohexadiamine complexes of some diorganotin,mono-organtotin and stannic carboxylates: Synthesis and spectral properties

o-Cyclohexadiamine (the base component of tetraplatin) adducts of Ph₂Sn(OCOCH₃)₂, nBu₂Sn(OCOH₃)₂, (PhCH₂)₂Sn(OCOCH₃)₂, PhSn(OCOCF₃)₃, BuSn(OCOCH₃)₃ and Sn(OCOCH₃)₄ have been synthesized and characterized by elemental analysis and spectroscopy. The compounds appear to be the first such adducts in their class.     

Synthesis,structure and spectroscopic properties of some thiosemicarbazone complexes of platinum

Reaction of salicyldehyde thosemicarbazone (H₂L¹), 2-hydroxyacetophenone thiosemicarbazone (H₂L²) and 2-hydroxynapthaldehyde thiosemicarbazone (H₂L³) (general abbreviation H₂L, where H₂ stands for the two dissociable protons, one phenolic proton and one hydrazinic proton) with K₂[PtCl₄] afforded a family of polymeric complexes of type [{Pt(L)}_n]. Reaction of the polymeric species with two monodentate ligands (D), viz. triphenylphosphine (PPh₃) and 4-picoline (pic), yielded complexes of the type [Pt(L)(D)]. These mixed-ligand complexes were also obtained from the reaction of the thiosemicarbazones with [Pt(PPh₃)₂Cl₂] and [Pt(pic)₂Cl₂]. The crystal structure of [Pt(PPh₃)(L²)] has been determined. The thiosemicarbazone ligands are coordinated, via dissociation of the two protons, as dianionic tridentate O,N,S-donors. The [Pt(L)(D)] complexes show characteristic ¹H NMR spectra and intense absorptions in the visible and ultraviolet region. They also fluoresce in the visible region at ambient temperature.     

Synthesis, crystal structure and optical limiting properties of some W---Se---Cu clusters

A nest-shaped cluster [(C₄H₉)₄N]₂[WOSe₃Cu₃Br_1.67Cl_1.33] (1) and a cage-shaped cluster [(C₄H₉)₄N]₃[WSe₄Cu₃Br₂Cl₂] (2) were synthesized and their structures were determined by single-crystal X-ray diffraction. It was found that cluster 1 showed better optical limiting properties under an 8 ns pulsed laser at 532 nm but poorer optical limiting properties under a 35 ps pulsed laser compared with its analogue [(C₄H₉)₄N]₂[MoOS₃Cu₃BrCl₂]. The influence of the peripheral ligands of the cluster to the optical limiting properties was also discussed.     

十八烷基取代吲哚啉螺吡喃衍生物的合成及光谱性质

本文合成了十种新的十八烷基取代的吲哚螺吡喃衍生物,拟进一步研究这类化合物在LB膜中的光致变色性质.     

Synthesis, structure, and spectral luminescent properties of novel 1,2,4-triazole derivatives containing benzthiazole group

Novel derivatives of 1,2,4-triazol with benzthiazole fragment have been prepared, including Cu(II) and Be complexes. Their structure and spectral luminescent properties have been investigated. With ohydroxyphenylbenzthiazolyl-1,2,4-triazole as an example, the density functional theory has been applied to find the stable conformers with different structures of coordination nodes, stabilized by intramolecular hydrogen bonds between hydroxyl group hydrogen and either triazole of benzthiazole nitrogen.     

Synthesis, structure and some properties of zirconium phosphate/oxide support compositions

Deposited zirconium phosphate samples on the base of silica and titania have been prepared using the sol?Cgel and mechanochemical methods. Porous structure, phase composition, and electrokinetic parameters have been studied by means of nitrogen adsorption?Cdesorption, XRD, DTA-TG, FTIR, electrophoresis, and potentiometric titration. The compositions possess varied parameters of porous structure, structure of deposited phase, and electrokinetic properties depending on support nature and synthesis conditions.     

Synthesis,structure, and biological properties of N-oxides of some 2-substituted quinoxalines and pyrazines

2-Methoxy- and 2-hydroxy-substituted quinoxaline and pyrazine N,N-dioxides and N-oxides of a number of quinoxaline-2-carboxylic acid derivatives were synthesized in order to study their biological activity. It is shown that the N-monoxides and N,N-dioxides of 2-hydroxy derivatives of quinoxaline exist primarily in the oxo form. Strong intramolecular hydrogen bonds were detected in the case of 1-N-oxides of 2-hydroxy and 2-carboxamido derivatives of quinoxaline. Substances with antibacterial and antituberculous activity were found among the synthesized compounds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 278–283, February, 1976.     

Synthesis,structure, spectral properties,and electrochemistry of bis(crown ether) containing 1,3-distyrylbenzenes

The reaction of tetraethyl [1,3-phenylenedi(methylene)]bis(phosphonate) with formyl derivatives of benzocrown-ethers or formyl derivatives of o-dimethoxybenzene lead to high yield formation of the respectful bis(crown ether) containing 1,3-distyrylbenzenes or tetramethoxy-substituted 1,3-distyrenebenzenes. NMR spectra and quantum-chemical calculations showed the prevalence of unsymmetrical syn/anti,(syn,anti),syn/anti-conformations in 1,3-distyrylbenzenes. 1,3-Distyrylbenzenes absorb in shorter wavelength spectral region and have a weaker fluorescence than 1,4-distyrylbenzenes. The difficulty in the electrochemical reduction of 1,3-distyrylbenzenes comparing with 1,4-distyrylbenzenes is due to a less effective conjugation system in the metaderivatives.     

Synthesis and spectral properties of hexafluoroaurates

It is established that krypton difluoride (KrF₂) interacts with metallic gold in anhydrous hydrogen fluoride (HF) in the presence of alkaline and alkaline-earth metal fluorides with the formation of complex hexafluoroaurates with the general formula M^IAu^VF₆ (M^I = Li, Na, K, Rb, Cs) and bis-hexafluoroaurates M^II(Au^VF₆)₂ (M^II = Mg, Ca, Sr, Ba). As a result of the subsequent interaction of bis-hexafluoroaurates with krypton difluoride, new coordination compounds with the composition M^II(Au^VF₆)₂ · nKrF₂ (M^II = Ca, Sr, Ba; n = 0–4) were synthesized. The Raman spectra were studied and a comparative analysis of the Raman spectra of the obtained compounds was performed. The possible variants of the structural transformation of the AuF ₆ ^? anions in compounds and the position and character of the chemical bond of the “guest” (KrF₂) in these compounds are discussed.     

Synthesis, molecular structure and spectral properties of quaternary ammonium derivatives of 1,1-dimethyl-1,3-propylenediamine

1,1-Dimethyl-3-oxo-1,4-diazepan-1-ium chloride (1) and 1,1-dimethyl-1-carboxymethyl-3-aminopropyl ammonium hydrochloride (2) have been obtained by the reactions of 1,1-dimethyl-1,3-propylenediamine with ethyl chloroacetate and chloroacetic acid, respectively. The products have been characterized by FTIR, Raman and NMR spectroscopy. B3LYP calculations have also been carried out. The screening constants for (13)C- and (1)H- atoms have been calculated by the GIAO/B3LYP/6-31G(d,p) approach and analyzed. The FTIR and NMR spectra of the investigated compounds 1 and 2 are in excellent agreement with the structures optimized by Density Functional Theory (DFT) calculations.     

Synthesis,structure, and reactivity of some N-phosphorylphosphoranimines

A large series of new N-phosphorylphosphoranimines that bear potentially reactive functional groups on both phosphorus centers were prepared by silicon-nitrogen bond cleavage reactions of N-silylphosphoranimines. Thus, treatment of the N-silylphosphoranimines, Me(3)SiN=P(Me)(R)X (R = Me, Ph; X = OCH(2)CF(3) and R = Me, X = OPh), with phosphoryl chlorides, RP(=O)Cl(2) (R' = Cl, Me, Ph), readily afforded the corresponding N-phosphoryl derivatives, R'P(=O)(Cl)-N=P(Me)(R)X, in high yields. Subsequent reaction with 1 or 2 equiv of the silylamine, Me(3)SiNMe(2), resulted in ligand exchange at the phosphoryl (P=O) group to give the P-dimethylamino analogues, R'P(=O)(NMe(2))N=P(Me)(R)X (R' = Cl, NMe(2), Me, Ph; R = Me, Ph; X = OCH(2)CF(3), OPh). These new N-phosphorylphosphoranimines (and one thiophosphoryl analogue) were obtained as thermally stable, distillable liquids and were characterized by NMR ((1)H, (13)C, and (31)P) spectroscopy and elemental analysis. One member of the series, Cl(2)P(=O)N=P(Me)(Ph)OCH(2)CF(3) (4), was also studied by single-crystal X-ray diffraction which revealed that the formal P(O)-N single bond [1.55(1) A] is shorter than the formal N=PR(2)X double bond [1.60(1) A]. Such structural features are compared to those of similar compounds and discussed in relationship to the unexpected thermolysis pathways observed for these N-phosphorylphosphoranimines, none of which produced poly(phosphazenes).     

Synthesis and spectral properties of mixedmeso-metallocenylporphyrins

A series of mixed porphyrins with different numbers of metallocenyl (ferrocenyl and cymantrenyl) and aryl (Ph and C₆F₅) groups at themeso-positions was obtained and characterized by¹H NMR, electronic absorption, and mass spectra. The downfield shift of NH signals as well as the bathochromic shift ofQ-bands can be attributed to a distortion of the porphyrin macrocycle upon the introduction of bulkymeso-substituents. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1045–1049, May, 1998.     

Synthesis, characterization, spectral and thermal properties of metal-hydrazinium nitrilotriacetates

Hydrazine derivatives of the monobasic nitrilotriacetate salts of zinc and alkaline earth metals have been prepared. IR absorption frequencies and thermal properties of these metal-hydrazinium nitrilotriacetates, (N₂H₅)M[N(CH₂COO)₃]·xH₂O have been defined. All the three -COOH appear to be dissociated in these salts. In thermal decomposition, these salts initially undergo dehydration followed by dehydrazination and via acetate intermediate step to metal oxycarbonates.