Triphenylarsine Oxide Research Articles

Drastic Enhancement of Photosensitized Energy Transfer Efficiency of a Eu(III) Complex Driven by Arsenic.

In this study, we focused on arsenic as a new potential motif for the ligand design of high-efficiency, luminous lanthanide complexes. A Eu3+ complex bearing triphenylarsine oxide had a photosensitized energy-transfer efficiency 7.9 times higher than that of a Eu3+ complex bearing triphenylphosphine oxide. This is mainly due to the heavy-atom effect of arsenic, which was supported by evaluating the photoluminescence spectra of their corresponding Gd3+ complexes.

Studying the metabolism of toxic chemical warfare agent-related phenylarsenic chemicals in vitro in cod liver

Large quantities of chemical warfare agents (CWAs), such as phenylarsenic chemicals, were disposed by sea-dumping after World War II. Nowadays, the release of these toxic chemicals from munitions poses a potential threat to living organisms. This study investigates the fate of these chemicals in fish by exposing selected CWA-related phenylarsenic chemicals and their oxidation products to cod (Gadus morhua) liver S9 fraction in vitro. Clark I (DA), Adamsite (DM) and their corresponding oxidation products as well as triphenylarsine oxide (TPA[ox]) and phenylarsonic acid (PDCA[ox]) were used as chemicals in in vitro experiments. Glutathione (GSH) conjugates of DA, DM and PDCA-related chemicals were found to be the most dominant metabolites, and methylated metabolites were detected as well, suggesting that these compounds are metabolised in the presence of cod liver enzymes. TPA[ox] was the only compound tested that did not form a GSH conjugate or methylated metabolite, indicating a different biotransformation pathway for this compound. Furthermore, hydroxylated metabolites were detected for each tested chemical. Due to their reactive nature, GSH conjugates may be difficult to detect in fish samples from CWA dumpsites. In contrast, both methylated and hydroxylated metabolites of phenylarsenic chemicals are promising target chemicals for the detection of CWA-related contamination in fish.

Extraction of Iron (III) by Tri-phenyl Arsine Oxide

Extraction of Iron (III) by Tri-phenyl Arsine Oxide

Acute toxicity of sea-dumped chemical munitions: luminating the environmental toxicity of legacy compounds

As a result of the disarmament of Germany after the Second World War, 65,000 tons of chemical munitions were dumped in the Baltic Sea. Approximately 13,000 tons containing chemical warfare agents (CWAs) of which 11,000 tons were dumped in the Bornholm Basin east of Bornholm. This paper addresses the ecotoxicity of compounds actually present in the Bornholm dumpsite by obtaining novel acute ecotoxicity data. EC50 values were successfully obtained for 12 CWAs from acute tests using Allivibrio fischeri (Microtox™). The three most toxic compounds were α-chloroacetophenone, 2-chlorovinylarsonic acid and 1,2,5-trithiepane having EC50 values of 11.20, 31.20 and 1170 μg L−1, respectively. A. fischeri demonstrated hormesis when exposed to triphenylarsine and triphenylarsine oxide at concentrations of 100 and 50 mg L−1, respectively. Four different mixtures were assessed including compounds which were dissolvable; a mixture of sulphur mustard degradation products, a mixture of the three most toxic sulphur mustard compounds, a mixture of organoarsenical degradation products and a mixture of all compounds. The mixtures deviate by a factor of 1.5–2.5 from the prediction of the concentration addition model and hence, the mixtures demonstrate no sign of synergism or antagonism. The compounds presented in this study are mainly CWA.

Discrete, Dispersible MnAs Nanocrystals from Solution Methods: Phase Control on the Nanoscale and Magnetic Consequences

Nanocrystals of thermodynamically stable alpha-MnAs (hexagonal NiAs-type) and metastable beta-MnAs (orthorhombic MnP-type) have been synthesized by the reaction of triphenylarsine oxide (Ph(3)AsO) and dimanganesedecacarbonyl (Mn(2)CO(10)) at temperatures ranging from 250 to 330 degrees C in the presence of the coordinating solvent trioctylphosphine oxide (TOPO). Morphologically, both alpha- and beta-MnAs nanoparticles adopt a core-shell type structure with a crystalline core and low-contrast noncrystalline shell. In contrast to prior studies on MnAs particles, disks, and films, the present bottom-up synthesis yields discrete, dispersible MnAs nanoparticles without a structural support. Even in the absence of epitaxial strain, the lattice parameters of the nanocrystals are decreased relative to bulk MnAs, resulting in a volume decrease of 0.35% in alpha-MnAs and 0.38% in beta-MnAs nanoparticles. In contrast to bulk MnAs, where the ferromagnetic phase transition upon warming through 313-317 K is concomitant with a structure change from ferromagnetic alpha- to paramagnetic beta-MnAs, powder X-ray diffraction studies suggest there is no conversion of alpha-MnAs to beta over the temperature range 298-343 K. Moreover, magnetic measurements suggest that both alpha- and beta-MnAs are ferromagnetic with T(C) approximately 315 K. Partial phase transformation of beta-MnAs nanoparticles into thermodynamically stable alpha-MnAs occurs slowly over time (i.e., months) at room temperature. However, there is no associated change in magnetization, suggesting the ferromagnetism observed in beta-MnAs is intrinsic and cannot be attributed to alpha-MnAs impurities.

Cytotoxicity of arsenic-containing chemical warfare agent degradation products with metallomic approaches for metabolite analysis

The arsenic metallome in African Green Monkey kidney cells is probed by measuring cytotoxicity, cellular arsenic uptake and speciation studies on arsenic-containing chemical warfare agent degradation products (CWDPs) during cell uptake. Inorganic arsenic compounds and methylated species also were studied during cell uptake as a means of providing cytotoxicity information relative to the CWDPs. The degradation products used were phenylarsine oxide (PAO), phenylarsonic acid (PAA), diphenylarsinic acid (DPAA), triphenylarsine (TPA) and triphenylarsine oxide (TPAO). These are the warfare agent’s primary degradation products. The parent warfare agents (red agents) are diphenylarsine chloride (DA or referred to as Clark I) and diphenylarsine cyanide (DC or Clark II), sternutator agents, sneezing gases able to cause bronchial irritation. Cytotoxicity levels and cellular uptake were compared to those of inorganic species: sodium arsenite, NaAsO2 [As(III)], sodium arsenateNa2HAsO4 [As(V)] and methylated arsenicals such as dimethylarsinic acid (DMA) and methylarsonic acid (MMA). The arsenic uptake was demonstrated in an African Green Monkey kidney cell line, CV-1. Quantification of lactate dehydrogenase activityreleased from damaged/dying cells was then measured via an LDH assay. The purpose of this study is to initially investigate toxicity to cells when exposed to different arsenic containing compounds over different concentrations and time ranges from 3 h to 24 h. Furthermore, exposed cells were then analyzed for different arsenic species by high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry to isolate and speciate arsenic fractions followed by nanoLC electrospray ionization mass spectrometry to analyze the molecular level changes of the arsenic based degradation products in the kidney cells. Metabolic changes to the arsenic species were found, and interestingly, at the lowest uptake levels, cytotoxicities were generally higher for the chemical warfare agent degradation products than the inorganic arsenic species.

Ascorbic Acid/Iodine and Triphenylphosphine/Iodine as Reducing Agents for the As(V)˭O Group

The scope of ascorbic acid/iodine and triphenylphosphine/iodine in methanol for the direct reduction of arsenic(V) compounds having the As˭O group has been investigated. Ascorbic acid/iodine reduces arsonic acids, diphenylarsinic acid (but not dimethylarsinic acid), and triphenylarsine oxide. The rates of reduction depend on the electronic effects of the ligands bound to arsenic and on the hydrogen-bonding strength of the species, when present. When the As(V) compound has an ‒NH 2 or an ‒NH 3 + group, the reduction product reacts with a ketonic form of dehydroascorbic acid, giving condensation product(s). Triphenylphosphine/iodine reduced slowly the zwitterionic o-aminophenylarsonic acid but reduced faster the hydrochloric acid salt of the same acid. It reduced dimethylarsinic acid as well because the powerful electron-withdrawing Ph 3 P +coordinated to As˭O seems to outweigh the electronic and hydrogen bonding effects.

The Reaction of Triphenylarsine Oxide with Ethyl Iodo‐acetate Leading to Triphenyl (Carboethoxy)methylarsonium Triiodide.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Direct measurement of lipid-soluble arsenic species in biological samples with HPLC-ICPMS

Lipid-soluble arsenicals (arsenolipids) occur in a wide range of biological samples where they may play a key role in the biosynthesis of organoarsenic compounds from inorganic arsenic. The study of these compounds has been hindered, however, by the lack of a suitable analytical technique able to separate and measure the various lipid species. As a source of arsenolipids, we used 10 crude fish oils from various regions of the world. Total arsenic analyses on the fish oils, performed with ICPMS following acid digestion with microwave-assisted heating, gave concentrations from 4.3 to 10.5 mg As kg(-1). All of the arsenic was soluble in non-polar solvents such as hexane. Analysis of the fish oils for arsenolipids was performed by normal phase HPLC-ICPMS with various mixtures of organic solvents as mobile phases. Inherent problems of instability associated with the introduction of organic solvents to the plasma were overcome by the use of reduced column flow, a chilled spray chamber, and the addition of oxygen directly to the plasma. All ten fish oils appeared to contain the same 4-6 major arsenolipids, but in varying amounts depending on the origin of the fish. Further chromatography with both normal phase and reversed-phase conditions on some of the oils indicated the presence of many more minor arsenolipids. Quantification was achieved by external calibration against triphenylarsine oxide or triphenylarsine sulfide, and the sum of species following HPLC of the oils matched well the total arsenic results (92-107%). The method was applied to samples of food supplements (fish oil capsules) and a packaged food product (cod liver) whereby arsenolipids were measured and found to be significant arsenic constituents. This study represents the first attempt to directly measure intact arsenolipids and, with appropriate sample preparation, may be suitable for quantitative measurement of these arsenicals in a range of biological samples, including foodstuffs.

Donor-Acceptor Reactions of Anhydrous Uranium Tetrachloride with Organic O-Bases

Reactions of anhydrous uranium tetrachloride with tributyl phosphate, dimethyl sulfoxide, diisoamyl methylphosphonate, hexamethylphosphoramide, diamyl sulfoxide, trioctylphosphine oxide, triisoamylphosphine oxide, dioctoxyphenyl selenoxide, diphenyl selenoxide, triphenylarsine oxide, and trioctylamine oxide in acetone and acetophenone were studied. The 1 : 1 and 1 : 2 complexes were revealed by conductometric titration in acetone and acetophenone solutions. The enthalpies of donor-acceptor reactions of O-bases with UCl4 in acetone and acetophenone were determined. These enthalpies in acetone linearly depend on the donor number of the O-base.

Coordination complexes of molybdenum with 3,6-di-tert-butylcatechol. Addition products of DMSO, pyridine N-oxide, and triphenylarsine oxide to the putative [MoVIO(3,6-DBCat)2] monomer and self-assembly of the chiral [(MoVIO(3,6-DBCat)2)4] square.

Molybdenum complexes of 3,6-di-tert-butylcatechol have been prepared from the reaction between [Mo(CO)(6)] and 3,6-di-tert-butyl-1,2-benzoquinone. A putative "[MoO(3,6-DBCat)(2)]" monomer is assumed to form initially by reaction with trace quantities of oxygen. Condensation of the reaction mixture leads to the formation of oligomeric products, including the [(MoO(3,6-DBCat)(2))(4)] chiral square isolated by chromatographic separation. Molybdenum centers at the corner of the square are bridged by oxo ligands centered along edges. Four-fold and inversion crystallographic symmetry gives tetramers as either LambdaLambdaLambdaLambda or DeltaDeltaDeltaDelta isomers, and the crystal structure consists of parallel columns of squares with the same chirality. Addition of O-Subst (O-Subst = dmso, pyridine N-oxide, triphenylarsine oxide) ligands to [MoO(3,6-DBCat)(2)] occurs selectively to give cis-[MoO(O-Subst)(3,6-DBCat)(2)] products. All three addition complexes are fluxional in solution. The temperature-dependent stereodymanic behavior of [MoO(dmso)(3,6-DBCat)(2)] has been shown to occur via a trigonal prismatic intermediate (Bailar twist) that conserves the cis disposition of oxo and dmso ligands. Electrochemical and chemical reduction reactions have been investigated for [MoO(dmso)(3,6-DBCat)(2)] with interest in displacement of SMe(2) with formation of cis-[MoO(2)(3,6-DBCat)(2)](2-). Cyclic voltammetry shows an irreversible two-electron reduction for the complex at -0.852 V (vs Fc/Fc(+)). Chemical reduction using CoCp(2) was observed to give a product with an electronic spectrum that is generally associated with cis-[MoO(2)(Cat)(2)](2-) complexes. Structural characterization revealed that the product was [CoCp(2)][MoO(3,6-DBCat)(2)], possibly formed as the product of dmso displacement upon one-electron reduction of [MoO(dmso)(3,6-DBCat)(2)].

The reaction of triphenylarsine oxide with ethyl iodo‐acetate leading to triphenyl (carboethoxy)methylarsonium triiodide

AbstractNew data are presented for some processes accompaning “retro‐Arbuzov” reaction of tertiary arsine oxides with halogen‐containing reagents. Triphenyl (carboethoxy)methylarsonium triiodide 10a was obtained in the reaction of triphenylarsine oxide 1a with excess of ethyl iodoacetate 2a. The structure of 10a was established by X‐ray single crystal diffraction. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:482–485, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20050

Uranyl polyhalides. Molecular structure of [UO 2(OAsPh 3) 4](Br 3) 2 and [UO 2(OPPh 3) 4](I 3) 2

Uranyl trihalides of general formula [UO 2L 4](X 3) 2 (L=hexamethylphosphoramide (HMPA), triphenylphosphine oxide (OPPh 3), triphenylarsine oxide (OAsPh 3); X=Br, I), along with some other higher polyiodides, have been prepared by reacting UO 2X 2· nH 2O with X 2 and L in methanol or acetonitrile. The molecular structures of [UO 2(OAsPh 3) 4](Br 3) 2 and [UO 2(OPPh 3) 4](I 3) 2 have been established by X-ray diffraction analysis. 31P NMR spectra are consistent with the existence of conformational isomers in solution for cations bearing HMPA and OPPh 3.

Synthesis of Arsenical Adduct: Synthesis and Transformation of Dimercapto Compound to Arsenical Adduct

Reaction of isothiocyanates with thioamide in presence of pyridine afforded 1,3-dimercapto substrates in good yield. Adipoin reacts with phenylarsine oxide and triphenylarsine to give the bicyclic 1,3,2-dioxarsole derivatives. A variety of 1,3,2-arsadithiolane derivatives were obtained by reaction of 1,3-dimercapto substrate with arsenic trioxide, phenylarsine oxide, triphenylarsine triphenylarsine oxide in ethanol or better in chloroform.

Synthesis, Spectra and Crystal Structure of Tetrakis(Triphenylarsine Oxide)Iron(III)-μ-Oxo-Tribromoiron(III) Tetrabromoferrate(III)-Acetonitrile

The oxidation of triphenylarsine with dioxygen in reaction systems containing some iron compound and Br- anions in acetonitrile leads to the formation of a novel unsymmetrical oxo-bridged diiron(III) complex [(OAsPh3)4 Fe(μ-O)FeBr3]+ [FeBr4]- ·CH3CN, where OAsPh3 is triphenylarsine oxide. The title complex is also formed by direct reaction of iron(III) bromide and OAsPh3 with dioxygen in acetonitrile solution. The crystal structure of the complex was solved by X-ray diffraction techniques. The cation contains two unsymmetrical species with an Fe-O-Fe bond angle of 159.2(2)°; one iron atom is pentacoordinated by four OAsPh3 ligands and a γ-oxo ligand which connects the tetracoordinated Fe atom with the FeBr3O chromophore. Structural parameters and IR spectra of similar complexes are compared and discussed.

Benchmark compounds. Structures of cobalt(II) complexes of triphenylphosphine- and triphenylarsine oxides

The structures of the Co(OPPh3)2Cl2, Co(OPPh3)2Br2, Co(OPPh3)2I2, Co(OAsPh3)2Br2 and Co(OAsPh3)2(NO3)2 complexes have been determined by X-ray diffraction methods; all have pseudo-tetrahedral co-ordination for cobalt.

Trichloro-bridged diruthenium (III,III) complexes: X-ray isomorphous structures of [Ph3X=O···H···O=XPh3][Ru2Cl7(XPh3)2]·0.5(CH2Cl2)(H2O)(X = As or P)

The triply chloro-bridged binuclear complexes [Ph3X=O···H···O=XPh3][Ru2Cl7(XPh3)2]·0.5(CH2Cl2)(H2O) (X = As or P) were obtained from [RuCl3(XPh3)2DMA]·DMA (DMA = dimethylacetamide) CH2Cl2/Et2O solution. The structures were characterized by X-ray diffraction studies. The complexes are formed from two Ru atoms bridged by three chloride anions. The two ruthenium atoms are also coordinated to two non-bridging Cl atoms and an AsPh3 or PPh3 ligand respectively. As an interesting feature, the cations of these complexes are protons, trapped in a very short hydrogen bond between two triphenylarsine or triphenylphosphine oxide molecules.

Catalytic asymmetric epoxidation of enones using La-BINOL-triphenylarsine oxide complex: structural determination of the asymmetric catalyst.

The catalytic asymmetric epoxidation of enones using the La-BINOL-Ph(3)As=O complex generated from La(O-i-Pr)(3), BINOL, and Ph(3)As=O in a ratio of 1:1:1 is described herein. Using 1-5 mol % of the asymmetric catalyst, a variety of enones, including a dienone and a cis-enone, were found to be epoxidized in a reasonable reaction time, providing the corresponding epoxy ketones in up to 99% yield and with more than 99% ee. The possible structure of the actual asymmetric catalyst has been clarified by various methods, including X-ray crystal structure analysis. This is the first X-ray analysis of an alkali-metal free lanthanoid-BINOL complex. Although La(binaphthoxide)(2)(Ph(3)As=O)(2) (7) was observed as the major complex in the complexes' solution, generated from La(O-i-Pr)(3), BINOL, and Ph(3)As=O in a ratio of 1:1:1, the possible active species turned out to be the La-BINOL-Ph(3)As=O complex in a ratio of 1:1:1. A probable reaction mechanism of the catalytic asymmetric epoxidation of enones is also proposed, suggesting that preferential formation of a heterochiral complex is the reason for asymmetric amplification. Moreover, the interesting role of La(O-i-Pr)(3) for accelerating the epoxidations while maintaining high ee's is discussed.

CRYSTAL STRUCTURES OF BIS(TRIPHENYLPHOSPHINE OXIDE)TRIBUTYLTIN AND BIS(TRIPHENYLARSINE OXIDE)TRIBUTYLTIN TETRAPHENYLBORATES

Article CRYSTAL STRUCTURES OF BIS(TRIPHENYLPHOSPHINE OXIDE)TRIBUTYLTIN AND BIS(TRIPHENYLARSINE OXIDE)TRIBUTYLTIN TETRAPHENYLBORATES was published on June 1, 2001 in the journal Main Group Metal Chemistry (volume 24, issue 6).

Bacterial release of arsenic ions and organoarsenic compounds from soil contaminated by chemical warfare agents

The objective of this paper was to investigate possible participation of microorganisms in the release of soluble arsenical compounds from organoarsenic warfare agents in contaminated soil. A number of bacterial strains were isolated with high resistance against As 3+ and As 5+ ions which are able to degrade the water insoluble compounds triphenylarsine (TP) and triphenylarsineoxide (TPO). These strains belong to different genera of bacteria. Release of arsenic ions and soluble organoarsenic compounds from soil by the activity of autochthonic soil bacteria and a mixture of the isolated pure cultures was demonstrated by percolation experiments with undisturbed soil samples (core drills) from the contaminated site. This release increased after addition of nutrients (mineral nitrogen and phosphorus, sodium acetate and ethanol) and is nearly independent of the percolation temperature (5°C and 22°C). These results show that bacteria play an important role in the release of arsenical compounds from organoarsenic warfare agent contaminated soil. This release is limited by shortage of water and, above all, of nutrients for the microorganisms in the sandy forest soil. These results are important both for the management and security and possibly for bioremediation of military waste sites containing similar contaminations. Furthermore, this is the first report on bacterial degradation of organoarsenic warfare compounds.