Triphenylarsine Oxide Research Articles

The chemistry of uranium. Part 36. Synthesis and characterization of some novel triphenylarsine oxide complexes of UI 4

The reaction between UI 4 and triphenylarsine oxide (tpao) has been studied in non-aqueous solution. A number of solid complexes have been isolated, viz. α-UI 4tpao 2, β-UI 4tpao 2, UI 4tpao 4 and UI 4tpao 6. The room temperature stable UI 4tpao 2 (α form) proved not to be the trans-octahedral species as commonly found for UCl 4 and UBr 4, but an auto- ionized solid, viz. [UI 2tpao 4] [UI 6]. The properties of these species are discussed and compared to their chloro- and bromo-analogues.

ChemInform Abstract: Structure and Bonding in Octahedral Uranium(IV) Complexes of the Type UX4·2L (X = Halogen, L = Unidentate Neutral Oxygen Donor). Part 2. Crystal Structures of Tetrachlorobis(tris(pyrrolidinyl)phosphine oxide)‐, Tetrachlorobis(di‐isobutyl sulphoxide)‐, and Tetrabromobis(triphenylarsine oxide)‐uranium(IV)

ChemInformVolume 18, Issue 9 Physical Organic Chemistry ChemInform Abstract: Structure and Bonding in Octahedral Uranium(IV) Complexes of the Type UX4·2L (X = Halogen, L = Unidentate Neutral Oxygen Donor). Part 2. Crystal Structures of Tetrachlorobis(tris(pyrrolidinyl)phosphine oxide)-, Tetrachlorobis(di-isobutyl sulphoxide)-, and Tetrabromobis(triphenylarsine oxide)-uranium(IV) J. F. DE WET, J. F. DE WET Chem. Dep., Univ. Port Elizabeth, Port Elizabeth 6000, S. Afr.Search for more papers by this authorM. R. CAIRA, M. R. CAIRA Chem. Dep., Univ. Port Elizabeth, Port Elizabeth 6000, S. Afr.Search for more papers by this author J. F. DE WET, J. F. DE WET Chem. Dep., Univ. Port Elizabeth, Port Elizabeth 6000, S. Afr.Search for more papers by this authorM. R. CAIRA, M. R. CAIRA Chem. Dep., Univ. Port Elizabeth, Port Elizabeth 6000, S. Afr.Search for more papers by this author First published: March 3, 1987 https://doi.org/10.1002/chin.198709050Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume18, Issue9March 3, 1987 RelatedInformation

Synthesis and characterization of a new coordination compound of gold(III) with triphenylarsine oxide(TPAsO)

Abstract A new solid coordination compound of the type 1:1 of TPAsO to gold(III) was prepared firstly by means of the extraction method, but only the coordination compound of the type 2:1 was obtained by the method of direct synthesis. It was found in polar solvents that the 1:1 type coordination compound could transform to that of the 2:1 type slowly. By the data of thermoanalyses, a mechanism was suggested for thermal decomposition of the above two coordination compounds.

Di-iodotetrakis(triphenylarsine oxide)uranium(IV) hexaiodouranate(IV). A new type of actinoid co-ordination compound

A new type of co-ordination compound having UX4L2 stoicheiometry consisting of both cationic and anionic six co-ordinated metal species has been isolated (M = uranium, X = iodide, and L = neutral donor ligand).

Oxidation studies of selected lanthanides in acetonitrile

Cerium(III), praseodymium(III) and terbium(III) nitrates were subjected to prolonged (3–24 h) ozonolysis in the presence of oxygen donor ligands in acetonitrile at 70 °C in an effort to stabilize the IV oxidation state of these metal ions. From spectroscopic and electrochemical studies it was determined that the lanthanides were oxidized to the IV oxidation state. Acetonitrile solutions of cerium(III) nitrate and cerium(III) chloride in the presence of triphenylarsine oxide (TPAsO) were also subjected to prolonged bubbling with air or oxygen at 70 °C. It was determined from spectroscopic studies that at least partial oxidation to the IV oxidation state of cerium occurred.

Oxidation Studies of the Plutonium (VI)/(IV) Couple with Triphenylarsine Oxide in Acetonitrile

Oxidation Studies of the Plutonium (VI)/(IV) Couple with Triphenylarsine Oxide in Acetonitrile

Spectroscopic and Electrochemical Studies of Tri- and Tetravalent Cerium and Americium with Triphenylarsine Oxide in Acetonitrile

Article Spectroscopic and Electrochemical Studies of Tri- and Tetravalent Cerium and Americium with Triphenylarsine Oxide in Acetonitrile was published on July 1, 1986 in the journal Radiochimica Acta (volume 39, issue 3).

Structure of the 1:1 adduct formed by p-nitrophenol with triphenylarsine oxide

Structure of the 1:1 adduct formed by p-nitrophenol with triphenylarsine oxide

Extraction of Zinc(ll) and Europium(lli) by Thenoyltrifluoroacetone and Triphenylphosphine or Triphenylarsine Oxides in Chloroform

Extraction of Zinc(ll) and Europium(lli) by Thenoyltrifluoroacetone and Triphenylphosphine or Triphenylarsine Oxides in Chloroform

ChemInform Abstract: Reactions of Uranium Hydride with Some Organic and Organometallic Compounds.

AbstractUH, reduces chloro‐, bromo‐, and iodo‐benzene to benzene (yield 44, 74, 20%, respectively) and biphenyl (4‐ 16%), nitrobenzene to azoxybenzene (12%) and azobenzene (8%), azoxybenzene to azobenzene (43%), and triphenylarsine oxide to triphenylarsine (56%) in boiling THF and/or in the absence of added solvent at 130‐ 170°C. In TH F, benzoyl Chloride gives low yields of butylbenzoate (6%) and benzil.

Structure and bonding in octahedral uranium(IV) complexes of the type UX4·2L (X = halogen, L = unidentate, neutral oxygen donor). Part 2. The crystal structures of tetrachlorobis[tris(pyrrolidinyl)phosphine oxide]-, tetrachlorobis(di-isobutyl sulphoxide)-, and tetrabromobis(triphenylarsine oxide)-uranium(IV)

The crystal structures of three complexes of uranium(IV) halides, UCl4·2tprpo (1), UCl4·2dibso (2), and UBr4·2tpao (3)[tprpo = tris(pyrrolidinyl)phosphine oxide, dibso = di-isobutyl sulphoxide, and tpao = triphenylarsine oxide], have been determined from three-dimensional X-ray diffraction data, and refined by full-matrix least-squares methods. For (1) the crystals are monoclinic, space group C2/c(final R= 0.046), for (2) monoclinic, space group P21/c(final R= 0.047), and for (3) monoclinic, space group P21(final R= 0.080). In each complex the uranium co-ordination is octahedral, with slight displacements (0.1 A) of the bromine atoms in (3) from their mean plane. The molecules in (1) and (2) have inversion symmetry. Compound (3) is isomorphous with the triphenylphosphine oxide analogue, UBr4·2tppo; the molecule is devoid of symmetry and adopts the same conformation as in the isomorph. The U–Cl distances are 2.620(4)A in (1) and 2.605(3)A in (2), while U–Br is 2.803(7)A in (3); U–O is 2.233(7)A in (1), 2.248(7)A in (2), and 2.12(3)A in (3). The U–X (X = halogen) and U–O bond lengths obtained in this work and in Part 1 of this series are compared with other estimates of these bonds in similar complexes. It is found (i) that the inverse relationship between the bond-length changes δ(U–X) and δ(U–O) previously noted for complexes containing the UO2X4 chromophore (‘axial–equatorial effect’) is maintained in the complexes studied here, thereby providing further evidence for the ligand–ligand repulsion effects which dominate the (largely ionic) bonding in such complexes, and (ii) that the data, when grouped according to generic ligand type, lend support for the donor-strength sequence AsO > PO > SO > CO based on chemical evidence.

Reactions of uranium hydride with some organic and organometallic compounds

Uranium hydride reduces chloro-, bromo-, and iodo-benzene to benzene and biphenyl, nitrobenzene to azoxy- and azo-benzene, azoxybenzene to azobenzene, and triphenylarsine oxide to triphenylarsine in boiling tetrahydrofuran and/or in the absence of added solvent at 130–170 °C. In tetrahydrofuran, benzoyl chloride gives low yields of butyl benzoate and benzil. A wide range of substrates, e.g. PhF, p-(O 2N) 2C 6H 4, PhCHO, C 5H 5Tl, and Ph 3PO, fails to react with UH 3.

Novel methods for the deoxygenation of triphenylarsine oxide to triphenylarsine

Two new and convenient methods using triphenylphosphite or sodium dithionite to deoxygenate triphenylarsine oxide to triphenylarsine are described.~(31)P NMR spectra was used to study the reactivity of triphenylphosphite and triphenylphosphine in deoxygenating triphenylarsine oxide,pyridine-N-oxide and dimethylsulfoxide and the influence of complex MoO_2(S_2CN(C_2H_5)_2)_2 on the reactivity.The mechanisms of the above reactions are briefly discussed.

Kinetics of Oxygen Transfer from Triphenylarsine Oxide to Triphenylphosphine in Molten State Monitored by Infrared Spectroscopy

Kinetics of Oxygen Transfer from Triphenylarsine Oxide to Triphenylphosphine in Molten State Monitored by Infrared Spectroscopy

NiBr 2 complexes with triphenylarsine oxide (Ph 3AsO). Two new interesting structures

The synthesis and crystal structure of two complexes resulting from interaction between NiBr 2 and triphenylarsine oxide (Ph 3AsO) is described. Green and orange complexes can be obtained from the blue, probably tetrahedral complex [NiBr 2(Ph 3AsO) 2], depending on the solvents used for recrystallization. NiBr 2·4[(C 6H 5) 3AsO]·8H 2O (green): M = 1650.2, P2 1/c, a = 13.731(2), b = 16.267(3), c = 17.647(2) Å, β = 112.04(1)°, V = 3651.4 Å 3, Z = 2, D x = 1.501 g cm -3, CuKα, λ = 1.54184 Å, μ = 38.67 cm -1, R = 0.039, 3741 unique reflections, 3203 with I > 3σ(I). NiBr 2·4[(C 6H 5) 3AsO]·3|2(C 6H 5CH 3)·H 2O (orange): M = 1663.7, P 1 , a = 12.647(8), b = 13.953(5), c = 22.853(6) Å, α = 90.91(3), β = 96.70(4), γ = 111.16(4)°, V = 3727.4 Å 3, Z = 2, D x = 1.482 g cm -3, MoKα, λ = 0.71073 Å, μ = 30.48 cm -1, R = 0.087, 8600 unique reflections, 4293 with I > 3σ(I). In the green complex the Ni(II) ion is sited on a center of symmetry and is octahedrally coordinated to six water molecules, hydrogen bonded to the Ph 3AsO molecules and to the bromide anions forming a second coordination sphere in a nearly octahedral arrangement. In the orange complex the cation is pentacoordinated with the four oxygen atoms of the Ph 3AsO ligands forming the basis of a tetragonal pyramid and with one Br - anion in the apical position. The absorption spectrum of the orange complex is compared with the spectra of other Ni(II) square pyramidal complexes described in the literature.

NiBr2complexes with triphenylarsine oxide (tpaso)

NiBr₂complexes with triphenylarsine oxide (tpaso)

ChemInform Abstract: POLYMERIC COMPLEXES FROM MOLYBDENUM TRIOXIDE, WITH NOTES ON DERIVATIVES AND RELATED COMPOUNDS

AbstractMoO3 löst sich in DMSO bei etwa 120°C zu einer Lösung, aus der zwei kristalline Phasen des polymeren Komplexes (Ia) erhalten werden können.

Mixed ligand extraction of cobalt(II) by thenoyltrifluoroacetone and triphenylphosphine or triphenylarsine oxides in chloroform

Extraction of Co(II) from perchlorate aqueous media by mixtures of thenoyltrifluoroacetone and triphenylarsine oxide or triphenylphosphine oxide in chloroform has been studied. It is found that the presence of these oxides enhances the extraction of Co(II). Synergic factors and formation constants were calculated and interpreted in the light of the electron donating properties of these oxides.

Polymeric complexes from molybdenum trioxide, with notes on derivatives and related compounds

Molybdenum trioxide dissolves in dimethyl sulphoxide (dmso) to give a solution from which the polymeric complex [{MoO3(dmso)1.33}n](1a) may be crystallised. It also reacts with pyridine N-oxide (pyo), triphenylarsine oxide, and pyridine (py) to give insoluble polymeric complexes [{MoO3(pyo)}n](2), [{MoO3(AsPh3O)0.5}n](3), and [{MoO3(py)}n](4). The solubility of (1a) enables its conversion to (2), (3), or (4). Another compound, [{MoO3(AsPh3O)}n](5) has been obtained from the MoVI acetylacetonate complex [MoO2(acac)2]. Evidence on the constitution of the insoluble compounds comes from i.r. spectra and X-ray diffractograms, with the ‘white’ and ‘yellow’ molybdic acids, [{MoO3(OH2)}n] and [{MoO3(OH2)}n]·nH2O respectively, providing reference structures. The molybdenum co-ordination environment comprises the ligand opposite a single terminal oxygen, along with four bridging atoms, as in the yellow form of the acid. The formation of these compounds is considered in relation to the simpler Mo–O–Mo bridge-cleavage reaction shown by the ‘digol’ compound [{MoO2(deg)}n](H2deg = diethylene glycol), to give complexes of the type [MoO2(deg)L]. Solutions of (1a) react with hydroxylic compounds in the presence of triethoxymethane as condensing agent. Products obtained from 2-amino-2-methylpropane-1,3-diol and 2-hydroxymethy1-2-methylpropane-1,3-diol are reported.

THE REACTION OF TETRACHLORO-o-BENZOQUINONE WITH THE SULFIDES OF TRIPHENYLARSINE AND TRIPHENYLSTIBINE

Abstract The reaction of tetrachloro-o-benzoquinone (1) with triphenylarsine sulfide gives a hydrogen-bonded complex of the corresponding hydroquinone and triphenylarsine oxide (5). The same quinone reacts with triphenylstibine sulfide yielding the cyclic adduct (9). In both cases, elemental sulfur is the other product. Possible reaction mechanisms are considered and the structural assignments are based on analytical, chemical and spectroscopic results.