- Hypercoordinated eka-tin materials with dangling aryl-methoxy and -methylthio ligands exhibiting intramolecular secondary bonding and aryl bond stabilization in reactions with organotin chlorides
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The syntheses of [2-(CH3ECH2)C6H4]PbPh3-nCln, (n = 0, E = O (4), E = S (5); n = 1, E = O (6), E = S (7); n = 2, E = O (8), are described. NMR and single crystal data illustrate significant Pb?E interactions increasing as n progresses from 0 to 2. The Pb?E interactions stabilize the Pb-aryl bonding to the extent that the reactions of 4 and 5 with Me2SnCl2 result in interchange of a Ph group and Cl to produce 6 and 7, respectively, together with Me2PhSnCl. This journal is
- Arias-Ugarte, Renzo,Metta-Maga?a, Alejandro J.,Ornelas, Alfredo,Pannell, Keith H.,Sharma, Hemant K.
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p. 16084 - 16091
(2021/11/27)
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- Kinetic and Computational Studies of Rhenium Catalysis for Oxygen Atom Transfer Reactions
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The rhenium(v)oxo dimer {MeReO(edt)}2 (edt≤1,2-ethanedithiolate) is an effective catalyst for the oxygen atom transfer (OAT) reaction from pyridine oxide and picoline oxide to triphenylarsine (Ph3As) as oxygen acceptor. Kinetics measurements were carried
- Ibdah, Abdellatif,Bakar, Heba Bani,Alduwikat, Salwa
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p. 149 - 159
(2018/03/09)
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- Synthesis, properties and application of electronically-tuned tetraarylarsonium salts as phase transfer catalysts (PTC) for the synthesis of gem-difluorocyclopropanes
-
Preparation of gem-difluorocyclopropane from α-methylstyrene and chlorodifluoromethane was investigated under basic two-phase conditions. Although simple tetraalkylammonium salts appeared uneffective as phase-transfer catalysts (PTC) for this purpose, tetraphenylarsonium chloride displayed moderate activity, and inspired studies of the phenomena. To improve its efficiency we synthesized set of electronically-tuned tetraarylarsonium analogues. Their preparation revealed interesting exchange process of aryl substituents on the arsonium center, whereas activity studies demonstrated a correlation of catalytic efficiency with electronic effects of the substituents. Two of the tetraarylarsonium catalysts were characterized by X-ray studies.
- Grudzień, Krzysztof,Basak, Tymoteusz,Barbasiewicz, Micha?,Wojciechowski, Tomasz M.,Fedoryński, Micha?
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supporting information
p. 106 - 110
(2017/04/11)
-
- Synthesis of novel pyrazole derivatives using organophosphorus, stibine, and arsine reagents and their antitumor activities
-
The reactions of 5-azido-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (azidopyrazole) with several classes of organophosphorus reagents: phosphonium ylides, Wittig-Horner reagents, dialkylphosphonates, trialkylphosphites, tris(dialkylamino)phosphanes, triphenylstibane, triphenylarsane, and Lawesson's reagent are reported. Structural reasoning for the new products was based on compatible analytical and spectral data. The cytotoxic activity of most of the new products was evaluated against human breast carcinoma cell line (MCF7) and human hepatocellular carcinoma cell line(HepG2). Certain tested compounds showed promising results.
- El-Sayed, Naglaa F.,Ewies, Ewies F.,El-Hussieny, Marwa,Boulos, Leila S.,Shalaby, ElSayed M.
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p. 765 - 776
(2016/07/27)
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- Versatile reagent Ph3As(OTf)2: One-pot synthesis of [P7(AsPh3)3][OTf]3 from PCl3
-
Compound Ph3As(OTf)2 as a pentacoordinated AsV Lewis acid readily forms dicationic Lewis acid/base ad-ducts upon addition of various Lewis bases. It also represents a stronger chloride-abstracting agent than Me3SiOTf and facilitates the reductive coupling of PCl3 in the presence of AsPh3 to the unprecedented cation [P7(AsPh3)3]3+ as triflate salt. This crystallographically characterized nor-tricyclane-type cation represents a P7R3-derivative with the most electron-withdrawing substituents, resulting in a pronounced effect on the structural parameters of the P7 core.
- Donath, Maximilian,Bodensteiner, Michael,Weigand, Jan J.
-
supporting information
p. 17306 - 17310
(2015/02/19)
-
- Studies on the peroxo complexes of thorium (IV) containing organic acids and amine bases
-
New peroxo complexes of Th(IV) have been synthesized and characterized by elemental analyses and various physicochemical techniques. The complexes were found to oxidize allyl alcohol and triphenylphosphine as well as triphenylarsine to their respective oxides. The molar conductance values and six fold coordination indicate that all the complexes are 1:1 electrolytes in dimethylsulphoxide revealing their ionic characters. The complexes display v(C=0) bands at-1625 cm-1 and v(C-O) bands at-1405 cm-1, significantly lower than the values of amino acid (-1630 cm-1 and -1412 cm-1) indicating the coordination of amino acids through their carboxylate anion. The Th(IV) complexes display v(M=O) modes in the region 910-999 cm-1. The broad band observed at about 3244-3386 cm -1 for v(N-H) modes indicates the coordination of amino group through nitrogen atom of amino acid. These are predominantly O-O stretching V 1, the symmetric M-O stretch V2 and the antisymmetric M-O stretch V3. The characteristic V1(O-O) modes of the complexes appear at 800-840 cm-1. It is observed that the V 1 mode decreases with the increase of atomic number of the metal in a particular group. The magnetic moment values of dioxothorium (IV) complexes revealed them to be diamagnetic in nature, suggesting there were no changes in the oxidation states of the metal ions upon complexation. The electronic spectral data of the complexes showed bands at 260-350 nm region due to the charge transfer band only.
- Nasrin, Jahanara,Saidul Islam
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experimental part
p. 65 - 71
(2010/08/07)
-
- Macroporous polystyrene-supported (diacetoxyiodo)benzene: An efficient heterogeneous oxidizing reagent
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A heterogeneous, cross-linked macroporous polystyrene-supported (diacetoxyiodo) benzene reagent has been prepared. This reagent is completely insoluble in all solvents and has a rigid pore structure that allows it to function without the need for swelling. Its utility in a variety of oxidation reactions has been demonstrated. Georg Thieme Verlag Stuttgart.
- Shang, Yongjia,But, Tracy Yuen Sze,Togo, Hideo,Toy, Patrick H.
-
-
- Comparative study of the phospha- and arsa-Wittig reaction using 1H, 75As and 17O NMR spectroscopy
-
The existence of oxaarsetanes during an arsa-Wittig reaction has been proved by 1H and 17O NMR spectroscopy. 75As NMR spectra were obtained from the corresponding arsonium salts and arsane oxides. The dynamic 1H NMR spectra of phospha- and arsaylides were compared. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Raeck, Christian,Berger, Stefan
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p. 4934 - 4937
(2007/10/03)
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- Osmium(IV) binuclear nonelectrolytic oxo-bridged carboxylates. Molecular structure of [Os2IV(μ-O)(μ-O2CCCl 3)2Cl4(PPh3)2] ·CH2Cl2
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The reactions between trans-[OsVIO2Cl 2L2] (L = PPh3, AsPh3, SbPh 3) and carboxylic acids RCO2H (R = CH3, C(CH3)3, CH2Cl, CCl3, CF 3) are studied. The resulting binuclear compounds were found to have the general formula [Os2IV(μ-O)(μ-O 2CR)2Cl4(L)2] (L = PPh3; R = CH3, C(CH3)3, CH2Cl, CCl 3, CF3, and L = AsPh3; R = CH3, CH2Cl, CCl3, CF3). X-ray diffraction analysis revealed that the [Os2IV(μ-O)(μ-O 2CCCl3)2Cl4(PPh3) 2]·CH2Cl2 complex crystallizes in a triclnic system with space group P1 ; a = 10.747(2) A, b = 19.291(4) A, c = 24.614(5) A, α = 100.08(3)°, β = 90.63(3)°, γ = 97.05(3)°, V = 4983.5(17) A3, Z = 4. The Os(μ-O)Os angle is 142.2(7)°. The interaction of trans-[Os VIO2Cl2(SbPh3)2] with all the acids under study is attended by intramolecular redox reaction resulting in SbCl2Ph3.
- Belyaev,Eremin,Simanova,Evreinova
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p. 262 - 268
(2008/10/09)
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- Reactions of trans-[OsO2Cl2L2] (L = PPh3, AsPh3, SbPh3) with acetic acid
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The possibility of reactions between trans-[OsO2Cl 2L2] (L = PPh3, AsPh3, SbPh 3) osmium(VI) complexes and glacial acetic acid to give osmium(IV) compounds of general formula [Os2/sub
- Belyaev,Eremin,Simanova,Evreinova
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p. 1907 - 1910
(2007/10/03)
-
- Stoichiometric and catalytic oxygen activation by trimesityliridium(III)
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Trimesityliridium(III) (mesityl = 2,4,6-trimethylphenyl) reacts with O2 to form oxotrimesityliridium(V), (mes)3Ir=O, in a reaction that is cleanly second order in iridium. In contrast to initial reports by Wilkinson, there is no evidence for substantial accumulation of an intermediate in this reaction. The oxo complex (mes)3Ir=O oxidizes triphenylphosphine to triphenylphosphine oxide in a second-order reaction with ΔH? = 10.04 ± 0.16 kcal/mol and ΔS? = -21.6 ± 0.5 cal/(mol·K) in 1,2-dichloroethane. Triphenylarsine is also oxidized, though over an order of magnitude more slowly. Ir(mes)3 binds PPh3 reversibly (Kassoc = 84 ± 3 M-1 in toluene at 20°C) to form an unsymmetrical, sawhorse-shaped four-coordinate complex, whose temperature-dependent NMR spectra reveal a variety of dynamic processes. Oxygen atom transfer from (mes)3Ir=O and dioxygen activation by (mes)3Ir can be combined to allow catalytic aerobic oxidations of triphenylphosphine at room temperature and atmospheric pressure with overall activity (~60 turnovers/h) comparable to the fastest reported catalysts. A kinetic model that uses the rates measured for dioxygen activation, atom transfer, and phosphine binding describes the observed catalytic behavior well. Oxotrimesityliridium does not react with sulfides, sulfoxides, alcohols, or alkenes, apparently for kinetic reasons.
- Jacobi, Bridey Grant,Laitar, David S.,Pu, Lihung,Wargocki, Michael F.,DiPasquale, Antonio G.,Fortner, Kevin C.,Schuck, Stephany M.,Brown, Seth N.
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p. 4815 - 4823
(2008/10/08)
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- Oxidations of ER3 (E = P, As, or Sb) by hydrogen peroxide. Methylrhenium trioxide as catalyst
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Catalytic and noncatalytic conversions of tertiary phosphines to their oxides by hydrogen peroxide have been investigated. The catalyst is methylrhenium trioxide, CH3ReO3. The kinetics were investigated in acetonitrile-water (1:1 by volume) at 25°C. Stepwise interactions between CH3ReO3 and H2O2 form CH3Re(η2-O2)(O)2(OI2). A, and CH3Re(η2-O2)2(O)(OH2), B. In CH3CN-H2O (1:1 v/v) the equilibrium constants are K1 = 13 ± 2 L mol-1 and K2 = 136 ± 28 L mol-1 at pH 1.0 and 25°C. The forward and reverse rate constants for the formation of A in this medium are k1 = 32.5 ± 0.3 L mol-1 s-1 and k-1 - 3.0 ± 0.2 s-1. Systematic changes in the substituents on phosphorus were made to vary the nucleophilicity of the phosphine and its cone angles; the kinetic effects are discernible, although they lie in a narrow range. Triphenylarsine and triphenylstibine were also studied, and their rates are within a factor of 2 of that for PPh3. The rhenium peroxides A and B show a small difference in reactivity. The bimolecular reactions between A and most of the phosphines have rate constants of the order 105 L mol-1 s-1. The kinetic data support a mechanism that allows nucleophilic attack of the substrate at the rhenium peroxides.
- Abu-Omar,Espenson
-
p. 272 - 280
(2007/10/02)
-
- Reaction of N-fluoropyridinium salts with Wittig reagents: A novel and convenient approach to symmetric trans-olefins
-
N-Fluoropyridinium salts were found to react with Wittig reagents containing electron-withdrawing groups to give olefins in 47-83% yield. The mechanism of this conversion is believed in involve single-electron transfer from Wittig reagent to N-fluoropyridinium cation.
- Kiselyov, Alexander S.
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p. 8951 - 8954
(2007/10/02)
-
- SYNTHESIS OF TRIPHENYLARSINE OXIDE BY OXIDATION OF TRIPHENYLARSINE BY OXYGEN UNDER THE CATALYTIC EFFECT OF IRON COMPOUNDS
-
Triphenylarsine oxide can be prepared conveniently by reacting triphenylarsine with dioxygen in the presence of iron compounds of the type of FeX3, and , (I3)2 (X = Br, SCN; Ph = C6H5), which act as catalysts.The last-mentioned compound was found most catalytically active.Conducted in acetonitrile solution at slightly elevated temperatures (60 to 70 deg C) and atmospheric pressure of dioxygen, the oxidation is selective and quantitative.
- Vancova, Vlasta,Ondrejkovicova, Iveta
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p. 2869 - 2871
(2007/10/02)
-
- ATOM TRANSFER AND EXCHANGE REACTIONS INVOLVING OXYGEN, SULFUR AND SELENIUM
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A systematic comparison has been made of the reaction conditions required to bring about the thermal transfer or exchange of Group 16 terminal elements between Group 15 molecular centers.Where reaction conditions were suitable, kinetic analyses have been performed, with the observed second-order behavior supporting the presumed bimolecular character of these reactions.
- Baechler, Raymond D.,Stack, Mary,Stevenson, Karen,Vanvalkenburgh, Virginia
-
-
- Acyl derivatives of main group metals: preparation of benzoyl derivatives of some group V and VI metals and metalloids
-
3,5-Dinitrobenzoyl chloride (1) adds oxidatively to triarylantimony to give the first benzoyl derivatives of antimony, ArSbCl.Triphenyl-phosphine and -arsine, and also bis(p-methoxyphenyl)tellurium(II) react with 1 in the same way.Conductivity and molecular weight data show that the benzoyl derivatives exist in solution as monomeric species.The metal-acyl bond in the compounds is stable towards MeOH, MeI, and CdX2.Reaction of 1 with triphenylbismuth leads to the cleavage of one Bi-Ph bond.Attempts to prepare the benzoyl derivative, Ph3PbCOC6H3(NO2)2, by the reaction of 1 with hexaphenyldilead were unsuccessful, but one Pb-Ph bond was cleaved of Ph4Pb in the presence of 1.
- Asthana, Anju,Srivastava, Ramesh C.
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p. 281 - 286
(2007/10/02)
-
- Alkaline Hydrolysis of Triphenylprop-2-ynylarsonium Bromide and Its Isomerized Products
-
Triphenylprop-2-ynylarsonium bromide (1) isomerizes readily in basic media to the non-terminal acetylenic isomer (3) via the allenic isomer (2).The results of alkaline hydrolysis of salt (1) and its isomerized products (2) and (3) have been reported.
- Khandker, M. N. I.,Ahmad, A.
-
-
- Mechanism of the oxidation of triphenyl derivatives of P, As, and Sb by peroxodiphosphate
-
Rate coefficients have been determined for the oxidation of Ph3M (M = P, As, Sb) by potassium peroxodiphosphate.The reaction is found to follow second-order kinetics, first order in each in the oxidant and Ph3M. +> has a pronounced accelerating effect on the reaction rate.An interesting dependence of the active species on the nature of the substrate has been observed.The reaction rate is influenced by changing the ionic strength of the medium.Acrylonitrile has no effect on the rate of oxidation.On the basis of the kinetic evidence, a general mechanism involving a bimolecular nucleophilic displacement of the substrate on the peroxo ion has been proposed.The relative rate order is found to be Ph3P > Ph3Sb > Ph3As and an explanation has been offered for the transposition of Ph3Sb and Ph3As.
- Srinivasan, C.,Pitchumani, K.
-
p. 2285 - 2289
(2007/10/02)
-
- SYNTHESIS OF VINYLIC EPOXIDES VIA ARSONIUM YLIDES
-
Vinylic epoxides were synthesized in high yields from allylic arsonium ylides and carbonyl compounds.
- Ousset, J.B.,Mioskowski, C.,Solladie, G.
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p. 4419 - 4422
(2007/10/02)
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- TRITOLYLARSONIUM AND TRIS(METHOXYPHENYL)ARSONIUM YLIDES THE EFFECTS OF ortho-SUBSTITUENTS IN TRIARYLARSONIUM GROUPS ON THE PROPERTIES OF YLIDES
-
A number of tritolylarsonium and tris(methoxyphenyl)arsonium cyclopentadienylides and other ylides have been prepared and their properties (basicity, NMR spectra, reactions with aldehydes and nitrosobenzene, acetylation, and methanolysis) have been investigated.Substituents in the m- or p-positions of triarylarsonium groups have little effect on properties, but o-substituents result in markedly lower reactivity and lower basicity, and these ylides were also more difficult to prepare.NMR spectra gave indication of crowding in some of these o-substituted ylides.The effects of the o-substituents are discussed. p-Methyl- and p-methoxy-substituents increased the proportion of anil to ketoxime formed in reactions with nitrosobenzene, but the o-methoxy analogue gave only ketoxime.
- Harris, Gordon S.,Lloyd, Douglas,MacDonald, William A.,Gosney, Ian
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p. 297 - 304
(2007/10/02)
-
- 1-Iodoacetylenes. Part 2. Formation Constants of their Complexes with Lewis Bases
-
Formation constants of the complexes of 1-iodoacetylenes (1)-(8) with Lewis bases (9)-(15) have been measured in solution by i.r. spectrophotometry.The stoichiometry of the complexes, the influence of the solvent on the equilibrium position, the existence of linear free energy relationships in the series of iodinated Lewis acids RI, where R=I, Br, Cl, CN, and CCX, and the relation between i.r. frequency shifts and stability constants are discussed.With any electron donor, 1-iodoacetylenes form less stable complexes than those formed by iodine cyanide.With hard bases, iodocyanoacetylene (8) and ethyliodopropiolate (7) give complexes wich are, respectively, more stable than and as stable as those with iodine; however, iodine complexes with soft bases are more stable.This is rationalized, in terms of empirical acidity scales, by the necessity to correlate the thermodynamic and spectroscopic properties of the RI complexes by a double scale equation.
- Laurence, Christian,Queignec-Cabanetos, Michele,Wojtkowiak, Bruno
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p. 1605 - 1610
(2007/10/02)
-
- Hydrogen-bond Assisted Observation of HCNH 1H N.M.R. Coupling in N-Methylanilines
-
Proton-proton HCNH coupling in high pKa N-methylanilines can be observed in solutions containing strong hydrogen-bond electron donors.
- Clark, James H.,Miller, Jack M.,Paone, Sergio
-
-
- Oxotrihalogenoselenates(IV): Preparation, Structure and Properties of P(C6H5)4SeOCl3, P(C6H5)4SeOBr3 and As(C6H5)4SeOBr3
-
The novel oxotribromoselenate(IV) SeOBr3(-) anion was prepared from the reaction of stoichiometric quantities of SeOBr2 and bromide in acetonitrile solution, and it was isolated as the tetraphenylphosphonium and -arsonium salts in crystalline form.For the synthesis of the analogous SeOCl3(-) as P(C6H5)4SeOCl3, SeCl4 was reacted in the presence of a small quantity of H2O with P(C6H5)4Cl in acetonitrile.Complete X-ray structural analyses of P(C6H5)4SeOCl3 (space group P, a = 10.981(3), b = 11.059(3), c = 10.358(3) Angstroem, α = 73.77(2) deg, β = 83.33(2) deg, γ = 80.51(2) deg, V = 1187.9(6) Angstroem3) and of P(C6H5)4SeOBr3 (space group P21/c, a = 11.719(4), b = 16.088(4), c = 13.124(4) Angstroem, β = 94.72(3) deg, V = 2466(1) Angstroem3) show dimeric centrosymmetric Se2O2Cl6(2-) and Se2O2Br6(2-) anions being present in the solid.In the anions two square-pyramidal (ψ-octahedral) SeOHal4 groups are connected through a common Hal-Hal edge.The axial oxygen ligands (Se-O: 1.597(4) and 1.584(6) Angstroem) cause a pronounced sterochemical trans-activation of the inert pairs at the Se atoms.As(C6H5)4SeOBr3 is isotypic with P(C6H5)4SeOCl3. - Key words: Oxohalogenoselenate, Crystal Structure, Selenium
- Krebs, Bernt,Schaeffer, Andreas,Hucke, Marita
-
p. 1410 - 1417
(2007/10/02)
-
- Effect of Bulky Size of Carbonyl Systems on Betaine Decomposition of Semi-stablized Arsonium Ylids
-
Reactions of substituted benzylidentriphenylarsenanes (2a-i) with 9-anthraldehyde and 9-fluorenone have been studied using benzene-sodamide, chloroform-sodium hydride and methanol-sodium ethoxide as solvent-base pairs.In all the cases olefins (5a-i and 6a-i) are formed exclusively.Variation of solvents and bases has no effect on the course of betaine decomposition formed by the nucleophilic attack of ylids on carbonyl systems.
- Gupta, K. C.,Srivastava, N.,Nigam, R. K.
-
p. 802 - 803
(2007/10/02)
-
- REACTIONS OF TRIPHENYLARSINE OXIDE WITH AQUEOUS HYDROGEN FLUORIDE: CRYSTAL STRUCTURE OF BIS(TRIPHENYLARSINE OXIDE)HYDROGEN(I) TETRAFLUOROBORATE
-
Fluorination of triphenylarsine oxide by aqueous hydrogen fluoride (1-40percent) in the absence of glass readily gives triphenylarsine difluoride.When the reaction with dilute (1percent) aqueous hydrogen fluoride is carried out in borosilicate glass apparatus, the glass participates in the reaction resulting in the formation of the crystalline 2:1 adduct 2Ph3AsO*HBF4.Crystals of this compound are monoclinic, P21/c, a = 12.926(4), b = 17.819(6), c = 14.994(4) Angstroem, β = 98.97(3) deg, Z = 4.The structure contains cations (1+) in which O....O is 2.44(2) Angstroem, and anions BF4-.
- Glidewell, C.,Harris, G. S.,Holden, H. D.,Liles, D. C.,McKechnie, J. S.
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p. 143 - 154
(2007/10/02)
-
- Is Oxygen Abstraction by Nucleophilic Reagents a Characteristic Reaction of Oxaziridines ?
-
The reaction of oxaziridines with nucleophilic reagents was studied.The summarized results are as follows. (1) The nucleophilic reactions occur preferentially on the nitrogen atom and the oxaziridine decomposes into a carbonyl compound and an ylide. (2) The reaction site shifts from nitrogen toward oxygen as the bulk of the ring substituents increases. (3) Cis isomers show faster reaction than trans isomers. (4) The carbon atom of the oxaziridine ring is completely inert to nucleophilic reagents.
- Hata, Yoshiteru,Watanabe, Masamichi
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p. 610 - 614
(2007/10/02)
-
- Organobismuth compounds. VI. Preparation and characterization of cationic complexes of triphenylbismuth(V) derivatives
-
Pentacoordinate cationic complexes of the types (Ph3BiL2)X2 and [(Ph3BiL)2O]X2, where L = DMSO, pyO, Ph3PO, or Ph3AsO and X = ClO4, BF4, or PF6, have been isolated and characterized by elemental analyses, infrared spectral, and conductance measurements. An unstable complex [Ph3Bi(Ph3AsO)2](NO3)2 has also been prepared and characterized by infrared spectroscopy. The Bi-O stretching frequencies for these complexes have been assigned, except for complexes containing Ph3PO. In dichloromethane, the complex [Ph3Bi(Ph3AsO)2]BF4 decomposes into Ph3BiF2 and Ph3AsOBF3 and the complexes [(Ph3BiL)2O](ClO4)2, where L = DMSO or pyO, appear to dissociate according to the equation [(Ph3BiL)2O](ClO4)2 ? [Ph3Bi(OClO3)]2O + 2L. No dissociation is indicated for other complexes. The complexes Ph3BiPh3Bi(Ph3AsO)2X2, where X = BF4 or PF6, form solvates with ketones such as acetone, diethyl ketone, and acetylacetone. Infrared and nmr data for these solvates indicate that the ketone is not coordinated to bismuth.
- Beaumont,Goel,Prasad
-
p. 944 - 947
(2007/11/06)
-