Two dimensional nuclear magnetic resonance analysis of bis(2,2 '-bipyridine)(2,2 '-bipyridine-4,4 '-dicarboxylic acid)ruthenium(II) hexafluorophosphate

The H-1 and C-13 nuclear magnetic resonance(NMR) spectra are reported for bis(2, 2'-bipyridine)(2, 2'-bipyridine-,4,4'-dicarboxylic acid) ruthenium(II) hexafluoruphosphate that has been used as a tagged molecule of electrochemiluminescent immunoassay. Because of the effect of Ru atom on ligands, it is difficult to assign its NMR spectra. BS' means of two dimensional H-1-H-1 COSY and H-1-C-13 COSY techniques, the H-1 and C-13 NMR spectra of bis (2, 2'-bipylidine) (2, 2'-bipyridine-4, 4-dicarboxylic acid) ruthenium(II) hexafluorophosphate are assigned completely. This provides a basis for NMR characterization of the nerv similar tagged molecules.

Analysis of 2D-nuclear magnetic resonance for Ru(2,2 '-bipyridine)(2)(4,4 '-dimethyl-2,2 '-bipyridine) (PF6)(2)

The H-1 and C-13 NMR spectra are reported for Ru(2,2'-bipyridine)(2)(4,4'-dimethyl-2,2'-bipyridine)(PF6)(2) that may be used as elechochemiluminescent species. Because of the effect of Ru atom on ligands and complex steric configuration, it is, difficult to attribute the spectra of the title molecular. By using 2D H-1-H-1 COSY and H-1-C-13 COSY methods, the proton and carbon-13 spectra are assigned completely. This also provides a basis for NMR characterization of the-similar new compounds.

Nuclear magnetic resonance spectral assignments of 2,2 '-bis(p-aminobenzoic ester)-1,1 '-binaphthyl

H-1 and C-13 nuclear magnetic resonance (NMR) spectra of 2, 2'-bis(p-aminobenzoic ester)-1,1'-binaphthyl were assigned and confirmed using 2D H-1-H-1 COSY, C-13-H-1 HETCOR and C-13-H-1 long-range HETCOR methods. This provided a basis for NMR characterization of the similar compounds.

Computer perception of topological symmetry by all-paths algorithm

During the development of our ESESOC system (Expert System for the Elucidation of the Structures of Organic Compounds), computer perception of topological symmetry is essential in searching for the canonical description of a molecular structure, removing the irredundant connections in the structure generation process, and specifying the number of peaks in C-13- and H-1-NMR spectra in the structure evaluation process. In the present paper, a new path identifier is introduced and an algorithm for detection of topological symmetry from a connection table is developed by the all-paths method. (C) 1999 Elsevier Science B.V. All rights reserved.

Chemical environment code and measure of molecular similarity

A new scheme for the code of chemical environments of compounds is described in this paper, and three molecular similarity methods have been used to select nearest neighbors from four different types of probe compounds. One of the methods is based on the C-13 NMR spectra. The second method is based on the code of chemical environments and molecular topological index A(x). The third approach, i.e. the Tanimoto coefficient, is also based on the code of chemical environments, but not to use the topological index. Five nearest neighbors for each probe compound using these three molecular similarity methods were determined and taken from the database of 7309 structures. The results indicate that the scheme of the chemical environment code and the method for similarity measure of intermolecules suggested in this study are reasonable. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

Synthesis of isotactic polystyrene with a rare-earth catalyst

Polymerization of styrene with the neodymium phosphonate Nd(P-507)/H2O/Al(i-Bu)(3) catalytic system has been examined. The polymer obtained was separated into a soluble and an insoluble fraction by 2-butanone extraction. C-13-NMR spectra indicate that the insoluble fraction is isotactic polystyrene and the soluble one is syndiotactic-rich atactic polystyrene. The polymerization features are described and discussed. The optimum conditions for the polymerization are as follows: [Nd] = (3.5-5.0) x 10(-2) mol/L; [styrene] = 5 mol/L; [Al]/[Nd] = 6-8 mol/mol; [H2O]/[Al] = 0.05-0.08 mol/mol; polymerization temperature around 70 degrees C. The percent yield of isotactic polystyrene (TY) is markedly affected by catalyst aging temperature. With increase of the aging temperature from 40 to 70 degrees C, TY increases from 9% to 48%. Using AlEt3 and Al(i-Bu)(2)H instead of Al(i-Bu)(3) decreases the yield of isotactic polystyrene. Different neodymium compounds give the following activity order: Nd(P-507)(3) > Nd(P-204)(3) > Nd(OPri)(3) > NdCl3 + C2HF5OH > Nd(naph)(3). With Nd(naph)(3) as catalyst, only atactic polystyrene is obtained. (C) 1998 John Wiley & Sons, Inc.

The structure and properties of 12-heteropolyacid of molybdenum and tungsten (H3PMo6W6O40) solvated by dimethyl ether

The crystal structure of H3PMo6W6O40 3C2H6O was determined by X-ray crystallography and refined to R = 0.0698 based on 2279 observed reflections to give unit cell parameters a = 16.48(2)Angstrom, c = 25.205(5)Angstrom , gamma = 120 degrees, hexagonal, space group R (3) over bar. The organic solvent molecules were characterized also by IR, H NMR spectra. Weak interaction existed between the organic solvent and the heteropoly acid in the secondary structure. The novel compound showed different behaviours in solubility, oxidizability and photosensitivity in comparison with classical dodeca heteropolyacid of molybdenum and tungsten. (C) 1998 Elsevier Science B.V.

The polymerization of methyl methacrylate with a new Nd(O-i-Pr)(3)-Al(i-Bu)(3) catalyst system

Methyl methacrylate (MMA) was polymerized with the rare earth coordination catalyst-system of Nd(O - i-Pr)(3) in toluene. The influences of various ligands in neodymium complexes, molar ratio of Al/Nd, catalyst concentration, catalyst aging time, solvents, the third component CCl4, temperature and time on the polymerization of MMA were studied. The results showed that the polymerization conversion reached more than 80% at a catalyst concentration of 9.2 x 10(-3) mol/L. The appropriate molar ratio of CCl4/Nd was 4. Hydrocarbon was preferred for the polymerzation to obtain a high conversion and a high <(M)over bar w> of PMMA. The H-1 NMR spectra of PMMA indicated that the lower the temperature, the higher the syndiotactic content of PMMA was obtained.

The synthesis of dendrimers bearing alkyl chains and their behavior at air-water interface

A new kind of amphiphilic polyether dendrimer bearing eight alkyl chains at the periphery were synthesized step by step using the convergent method. Their structures were confirmed by FT-IR spectra, H-1 NMR spectra and mass spectra etc. The pi-A isotherms, hysteresis and molecular area-time curves at air water interface were reported. These results showed that they could form stable monolayers at water surface.

Compatibility and specific interactions in poly(beta-hydroxybutyrate) and poly(p-vinylphenol) blends

The miscibility and specific interactions in poly (beta-hydroxybutyrate) (PHB)/poly(p-vinylphenol) (PVPh) blends were studied by differential scanning calorimetry(DSC) , fourier transform infrared(FTIR) spectrometer and high resolution solid state C-13 NMR, A single composition-dependent glass transition temperatures were obtained by DSC which indicate the blends of PHB/PVPh were miscible in the melt state, The experimental glass transition temperatures were fitted quite well with those obtained from Couchman-Karasz equation. The FTIR study shows that the strong intermolecular hydrogen bonding exists in blends of PHB with strong proton acceptor and PVPh with strong proton donor and is the origin of its compatibility. The CPMAS C-13 NMR spectra also show that the strong hydrogen bonding exists in PHB/PVPh blends. From the T-1 rho(H) relaxation time it follows that the blends of PHB/PVPh(40/60, 20/80) studied are completely homogeneous on the scale of about 3.2 nm.

Chlorination and oxidation of aromatic polyamides .2. Chlorination of some aromatic polyamides

The effects of chlorine on three kinds of aromatic polyamides: those not containing a substituent, those containing substituents, and those containing heterocyclic aromatic rings, were studied. The correlations between the chemical structures of polyamides and the reactivity to hypochlorous acid were examined by IR and C-13 solid-state NMR spectra before and after chlorination. It was found that the chlorination of polyamides depends not only on their chemical structures but also on chlorination conditions such as pH value and reaction time. Their response to chlorination corresponds to four types: ring-chlorination, no reaction, N-chlorination, and chain cleavage. (C) 1996 John Wiley & Sons, Inc.

Chlorination and oxidation of aromatic polyamides .1. Synthesis and characterization of some aromatic polyamides

The synthesis is described of some aromatic polyamides based on unsubstituted, and methyl-, carboxy-, and sulfo-substituted diamines by interfacial polycondensation. Some of them are crosslinked and some of them contain heterocyclic aromatic rings. Their chemical structures are characterized by IR and C-13 solid-state NMR spectra and the spectra are interpreted. (C) 1996 John Wiley & Sons, Inc.

Ansa-metallocene derivatives .2. Syntheses and structures of tetramethyldisiloxandiyl bis(1-indenyl and tetrahydroindenyl) zirconium dichlorides

The ansa-zirconocene derivative tetramethyldisiloxandiyl bis(1-indenyl) zirconium dichloride (1) has been prepared by the reaction of the dilithium salt of 1,3-bis(l-indenyl) tetramethyldisiloxane with ZrCl4 . 2THF, After catalytic hydrogenation, the corresponding tetrahydroindenyl complex (2) has been formed. Both 1 and 2 have been shown by H-1 NMR spectra to be the mixture of the cis(meso) and trans(rac) isomers, The pure trans isomers 1(l), 2(l) and cis isomer 2(c) were obtained by recrystallization, The crystal structures of 1(l) and 2(c) were determined by X-ray diffraction. Both crystals of 1(l) and 2(c) are monoclinics, belonging to space groups P2(1)/n(1(l)) and P2(1)/c(2(c)). In the unit cell of 2(c), one of the six-membered rings of the tetrahydroindenyl Ligands has two different conformations which have the same probabilities.

SYNTHESIS AND CHARACTERIZATION OF TRISUBSTITUTED HETEROPOLYTUNGSTOGERMANATES CONTAINING GROUP 3A ELEMENTS

Six new compounds, alpha,beta-KaHb[GeW(9)M(3)(H2O)(3)O-37]. xH(2)O(M = Al, Ga, In; a + b = 7) and alpha-K9H5[Ge2W18Ga6(H2O)(3)O-74]. 20H(2)O, were synthesized from the lacunary precursors a and beta-GeW9O3410- and characterized by elemental analysis, spectroscopy and electrochemistry. Tungsten-183 NMR spectra of the title complexes consist of two lines with intensity ratio 2:1 as expected for trisubstituted heteropoly anions. The intensity ratio of alpha-Ga compound is 1:2, which is different from others(a:1). With the help of FAB mass spectrum, we concluded that it is a dimer with D-3h structure in aqueous, and the others exist by monomers with C-3v structures.

SYNTHESES AND CHARACTERIZATION OF [(MU-CF3CO2)(2)LN(MU-CF3CHO2)ALR(2)CENTER-DOT-2THF](2) AND THEIR CATALYTIC ACTIVITIES FOR POLYMERIZATION OF SOME POLAR MONOMERS

Three new bimetallic complexes were synthesized and crystalized by reactions of (CF3CO2)(3)Ln With R(1) AlR(2)(Ln=Nd and Y, R(1)=H, R=i-C4H9; Ln=Eu, R=R(1)=C2H5) in tetrahydrofuran solution, and their crystal structures were determined using a X-ray diffraction method. The structures and the questions on valence state and noncoplanarity in the structures were confirmed and cracked by means of H-1 NMR and C-13 NMR spectra, especially by C-13-H-1 COSY 2D NMR technique. A general formula of molecules of the three rare earth complexes was defined as follows: [(mu-CF3CO2)(2)Ln(mu-CF3CHO2)AlR(2) . 2THF](2) A mechanism on the formation of the new complexes was also proposed through the following five steps: alkylating, beta-elimination (or hydrogenation), hydrogen transfer, linkage and association. Both Y-Al and Eu-Al complexes function as a catalyst in polymerization of MMA and ECH. The polymer obtained from the first monomer is mainly syndiotactic chain structure and the polymerization of the last monomer shows higher catalytic activity. The Y-Al complex also capable of ring-opening polymerization of THF in case of adding-vary small amount of ECH and a oxonium ion mechanism of THF polymerization was suggested from the analysis of THF polymer terminal.