Synthesis, structure and magnetic behavior of a new three-dimensional Manganese phosphite-oxalate: [C2N2H10][Mn-2(II)(OH2)(2)(HPO3)(2)(C2O4)]

A novel manganese phosphite-oxalate, [C2N2H10][Mn-2(II)(OH2)(2)(HPO3)(2)(C2O4)] has been hydothermally synthesized and its structure determined by single-crystal X-ray diffraction. The structure consists of neutral manganese phosphite layers, [Mn(HPO3)](infinity), formed by MnO6 octahedra and HPO3 units, cross-linked by the oxalate moieties. The organic cations occupy the middle of the 8-membered one dimensional channels. Magnetic studies indicate weak antiferromagnetic interactions between the Mn2+ ions. (C) 2009 Elsevier Inc. All rights reserved.

NMR relaxation study of disorder in condensed matter: solid solutions of betaine phosphate and phosphite

Proton NMR relaxation measurements have been carried out in anti-ferroelectric Betaine phosphate (BP), ferroelectric Betaine phosphite (BPI) and the mixed system BPI(1-x)BPx, at 11.4MHz and 23.3MHz from 300K to 80K for x=0.0, 0.25, 0.45, 0.85, and 1.0. The temperature dependence of spin lattice relaxation time T, exhibits two minima as expected from the BPP model in BP and BPI. The Larmor frequency dependence of T, in the mixed system is rather unusual and exhibits different slopes for the low temperature wings at the two frequencies, which is a clear experimental evidence of the presence of different methyl groups with different activation energies (E-a) indicating disorder.

New open-framework phosphate and phosphite compounds of gallium

Five new open-framework compounds of gallium have been synthesized by hydrothermal methods and their structures determined by single crystal X-ray diffraction studies. The compounds, C8N4H26]Ga6F4(PO4)(6)], I, C5N3H11]Ga3F2(PO4)(3)]center dot H2O, II, C6N3H19]Ga-4(C2O4)(PO4)(4)(H2PO4)]center dot 2H(2)O, III, Ga2F3(HPO4)(PO4)]center dot 2H(3)O, IV, and C3N2H5](2)Ga-4(H2O)(3)(HPO3)(7)], V, possess three-dimensional structures. All the compounds are formed by the connectivity between the Ga polyhedra and phosphite/phosphate units. The observation of SBU-6 (I and II) and spiro-5 (IV) secondary building units (SBUs) are noteworthy. The flexibility of the formation of gallium phosphate frameworks has been established by the isolation of two related structures (I and II) from the same SBU units but different organic amines. Some of the present structures have close resemblance to the gallium phosphate phases known earlier. The compounds have been characterized by CHN analysis, powder XRD, IR, and TGA. (C) 2011 Elsevier B. V. All rights reserved.

Polarization switching studies in ferroelectric glycine phosphite single crystals

Glycine Phosphite [NH3CH2COOH3PO3], abbreviated as GPI, undergoes a para-ferroelectric phase transition from the monoclinic symmetry P2(1)/a to P2(1) at 224.7 K. We report here a systematic study of the polarization switching process in this crystal. Growth of these crystals from aqueous solution has been undertaken employing both solvent evaporation and slow cooling methods. Hysteresis loop measurements along the polar b-axis yielded a spontaneous polarization value of 0.5 muC/cm(2) and a coercive field of 2.5 kV/cm. Conventional Merz technique was employed for polarization switching studies, wherein bipolar square pulses were applied to the sample to induce domain reversal. The transient switching pulse that flows through the sample on application of the field was recorded. The maximum switching time required for domain switching was measured both as a function of electric field and temperature. The experimentally observed switching curves were fitted with the model based on the Pulvari-Kuebler theory of nucleation and growth of domains. From the experimental data, the values of mobility and activation field were obtained. It was observed that switching process in this crystal is predominantly governed by the forward growth of domain walls in the high field region. However, switching process in GPI crystal was found to be slower than that found in other glycine based ferroelectric crystals.

Growth and characterization of ferroelectric glycine phosphite single crystals

Single crystals of a recent ferroelectric material, glycine phosphite were grown from aqueous solution employing the techniques of slow cooling and controlled evaporation. Powder X-ray diffraction studies as well as thermal analysis were carried out on the grown crystals. The morphology of the crystal has been determined using contact and optical goniometry. The mechanical hardness of the crystal was evaluated by Vickers indentation method. Thickness dependence of the dielectric properties has been investigated and the results can be interpreted in terms of a surface layer of lower dielectric constant.

Highly enantioselective conjugate addition of diethylzinc to acyclic enones with fine-tunable phosphite-pyridine ligands

A new series of fine-tunable phosphite-pyridine (P,N) ligands derived from (S)-2-amino-T-hydroxy-6,6'-dimethyl-1,1'-biphenyl and (S)-2-amino-2'-hydroxy-4,4',6,6'-tetramethyl-1,1'-biphenyl was employed in Cu(I)-catalyzed conjugate addition of diethylzinc to acyclic enones. Excellent enantioselectivities (up to 98% ee) and highly catalytic activities were achieved for a variety of acyclic enones.

Living polymerization of 1,3-butadiene by a Ziegler-Natta type catalyst composed of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite

Living characteristics of facilely prepared Ziegler-Natta type catalyst system consisting of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite have been found in the polymerization of 1,3-butadiene in hexane at 40 degrees C. The characteristics have been well demonstrated by: a first-order kinetics with respect to monomer conversion, a narrow molecular weight distribution (M-w/M-n = 1.48-1.52) of polybutadiene in the entire range of polymerization conversion and a good linearity between M-n and the yield of polymer. Feasible post-polymerization of 1,3-butadiene and block co-polymerization of 1,3-butadiene and isoprene further support the living natures of the catalyst bestowed with.

Fe(2-EHA)(3)/Al(i-Bu)(3)/hydrogen phosphite catalyst for preparing syndiotactic 1,2-polybutadiene

Polymerizing 1,3-butadiene into syndiotactic 1,2-polybutadiene with art iron(III) catalyst system has been investigated. Activity of the catalyst was affected by the type of cocatalyst alkylaluminum and the phosphorus compound as an electron donor, molar ratio of catalyst components, and their aging sequence and aging time of the catalyst. The microstructure and configuration of the polymer was decided by the catalyst components, the higher [Al]/[Fe] molar ratio tending to yield syndiotactic 1,2-polybutadiene, while the higher [P]/[Fe] molar ratio favors the formation of amorphous 1,2-polybutadiene.

Atmospheric pressure photoionization mass spectrometry as a tool for the investigation of the hydrolysis reaction mechanisms of phosphite antioxidants

The hydrolysis reaction mechanism of phosphite antioxidants is investigated by liquid chromatography-mass spectrometry (LC/MS). The phosphites were chosen because they differed in chemical structure and phosphorus content. Dopant assisted-atmospheric pressure photoionization (DA-APPI) is chosen as the ion source for (lie ionization of the compounds. [it our previous work, DA-APPI was shown to offer an attractive alternative to atmospheric pressure chemical ionization (APCI) since it provided background-ion free mass spectra and higher sensitivity [M. Papanastasiou, et al., Polymer Degradation and Stability 91 (11) (2006) 2675-2682]. In positive ion mode, the molecules are generally detected in their protonated form. In negative ion mode, the phosphites are unstable and only fragment ions are observed: these however, are characteristic of each phosphite and may be used for the identification of the analytes in complex mixtures. The analytes under investigation are exposed to accelerated humid ageing conditions and their hydrolytic pathway and stability is investigated. Different substituents around the phosphorus atom are shown to have a significant effect on the stability of the phosphites, with phenol substituents producing very hydrolytically stable structures. Alkanox P24 and PEP-36 follow a similar hydrolytic pathway via the scission of the first and then the second P-O-phenol bonds, eventually leading to the formation of phenol, Phosphorous acid and pentaerythritol as end products. HP-10 exhibits a rather different Structure and the products detected suggest scission of either the P-O-hydrocarbon or one of the P-O-phenol bonds. A phenomenon similar to that of autocatalysis is observed for all phosphites and is attributed to the formation of dialkyl phosphites as intermediate products. (C) 2008 Elsevier B.V. All rights reserved.

Direct Determination of Phosphite in Fertilizers by Amperometric Titration

Amperometric titration using two Pt microelectrodes for the determination of phosphite in fertilizers based on the oxidation of analyte by iodine is proposed. The influence of pH, buffer composition, temperature, and foreign species on the end point and titration time was investigated. For titrations carried out at 70 degrees C using the pH 6.8 phosphate buffer, samples containing ca. 0.4% (m/v) P(2)O(5) could be titrated with 0.050 mol L(-1) iodine titrant, and the end point determined by extrapolating the linear portions of the plot to their intersection coincided with the end point identified by spectrophotometry. Accuracy was checked for phosphite determination in five fertilizer samples. Results were in agreement at the 95% confidence level (paired t test) with spectrophotometry. Recoveries of phosphite added to fertilizer samples ranged from 97% to 102% regardless of the amount of spiking in several determinations. The relative standard deviation (n = 10) was 1.0% for a diluted sample containing 0.050 mol L(-1) Na(2)HPO(3).

THE ELECTROCHEMICAL OXIDATION OF (BENZYLIDENEACETONE)DICARBONYL(PHOSPHINE)IRON(0) AND (BENZYLIDENEACETONE)DICARBONYL(PHOSPHITE)IRON(0) COMPLEXES IN DIMETHYL FORMAMIDE

The electrochemical oxidation of (benzylideneacetone)dicarbonyl(phosphine)iron(0) and benzylideneacetone)dicarbonyl(phosphite)iron(0) complexes was studied by cyclic voltammetry and controlled potential electrolysis in 0.5 M NaClO4 (dimethyl formamide). The results suggest that the electrode process involves a complicated mechanism, the species formed in the first oxidation step being highly unstable and its decomposition producing free benzylideneacetone, free phosphine or phosphite, solvated iron(II) species and carbon monoxide which adsorbs on the platinum electrode. A linear relationship between E(p/2)ox and the ligand parameter P(L) was obtained with E(s) = 0.41 V and beta = 0.964, where E(s) and beta-denote electron-richness and polarizability of the metal centre, respectively.

Phosphite determination in fertilizers after online sequential sample preparation in a flow injection system

A flow injection spectrophotometric system is proposed for phosphite determination in fertilizers by the molybdenum blue method after the processing of each sample two times on-line without and with an oxidizing step. The flow system was designed to add sulfuric acid or permanganate solutions alternately into the system by simply displacing the injector-commutator from one resting position to another, allowing the determination of phosphate and total phosphate, respectively. The concentration of phosphite is obtained then by difference between the two measurents. The influence of flow rates, sample volume, and dimension of flow line connecting the injector-commutator to the main analytical channel was evaluated. The proposed method was applied to phosphite determination in commercial liquid fertilizers. Results obtained with the proposed FIA system were not statistically different from those obtained by titrimetry at the 95% confidence level. In addition, recoveries within 94 and 100% of spiked fertilizers were found. The relative standard deviation (n = 12) related to the phosphite-converted-phosphate peak alone was <= 3.5% for 800 mg L-1 P (phoshite) solution. Precision due to the differences of total phosphate and phosphate was 1.1% for 10 mg L-1 P (phosphate) + 3000 mg L-1 P (phosphite) solution. The sampling rate was calculated as 15 determinations per hour, and the reagent consumption was about 6.3 mg of KMnO4, 200 mg of (NH4)(6)Mo7O24 center dot 4H(2)O, and 40 mg of ascorbic acid per measurement.