Search

1. The photochemical reactions of cyclopentadienyltetracarbonylniobium with triphenylphosphine, triphenylstibine have been studied. The composition of the reaction products depends on the solvent used. 2. Cyclopentadienyltricarbonylniobium-triphenylphosphine, cyclopentadienyltricarbonylniobiumtriphenylarsine, and cyclopentadienyltricarbonylniobium-triphenylstibine, and also cyclopentadienyldicarbonylniobium-bis (triphenylphosphine), have been obtained and characterized.

Triphenylphosphine, triphenylarsine, triphenylstibine, and triphenylbismuthine have been evaluated as acceptors in oxygen transfer reactions involving 1-pyrroline-1-oxides. The first reagent especially offers a useful route from the nitrones to the corresponding pyrrolines.

The infrared spectrum of triphenylstibine is reported and assigned by comparison with the spectra of triphenylphosphine and triphenylarsine.

Paramagnetic tetrakis(2,6-dimethylphenyliso- cyanide)cobalt(II) perchlorate, [Co(CNR) 4 ](ClO 4 ) 2 , R  2,6-Me 2 C 6 H 3 , has been prepared from pentakis- (2,6-dimethylphenylisocyanide)cobalt(II) perchlorate hemihydrate, [Co(CNR) 5 ](ClO 4 ) 2 ·0.5H 2 O, in novel reactions with triphenylarsine and triphenylstibine. Analogous reaction with [Co(CNR) 5 ](BF 4 ) 2 ·0.5H 2 O produced only [Co(CNR) 5 ]BF 4 . Both [Co(CNR) 5 ]- X 2 ·0.5H 2 O, X  ClO 4 − , BF 4 − , can be recrystallized from CH 2 Cl 2 , CHCl 3 or CH 2 ClCH 2 Cl in 0.15–0.30 M initial concentration, to produce [Co(CNR) 5 ]X 2 ·S (S  adducted solvent) in good yield. Recrystallization of [Co(CNR) 5 ](ClO 4 ) 2 ·0.5H 2 O from dilute (C M ⩽ 5 X 10 −3 M) solution, however, produces [Co(CNR) 4 ](ClO 4 ) 2 ·S, while [Co(CNR) 5 ](BF 4 ) 2 · 0.5H 2 O regenerates the starting material. Recrystallizations from CH 3 CN or CH 3 NO 2 produce [Co(CNR) 5 ](ClO 4 ) 2 ·0.5H 2 O (concentrated solution) or no recovered product (dilute solution). Solid-state properties of magnetic susceptibilities, diffuse reflectance electronic spectra, and mull-infrared are investigated. Distorted square planar coordination of RNC in [Co(CNR) 4 ](ClO 4 ) 2 is suggested. Infrared v (ClO 4 ) strongly suggests monodentate ClO 4 − coordination in [Co(CNR) 4 ](ClO 4 ) 2 , or [Co(CNR) 4 (ClO 4 ) 2 ], while the possibility of weaker ClO 4 − coordination in [Co(CNR) 5 ](ClO 4 ) 2 ·0.5H 2 O is ambiguous. Isolation of [Co(CNR) 4 ](ClO 4 ) 2 is the first observed incident of significant difference between BF 4 − and ClO 4 − salts of Co(II)-arylisocyanide complexes.

Novel μ-oxo-bis(diphenylhydroxyantimony) di[2-(methylamino)ethoxide] (1) was obtained in the reaction of triphenylstibine oxide and 2-(methylamino)ethanol. Cyclic urethane derivatives were obtained by the reaction of 1 with CO2 or CS2 in good yields.

Triphenylantimony dicarboxylates (Ph3Sb(O2CR)2, where R=Me, CF3, Ph and CH2NH-Z) readily reacted with amines (R′NH2, where R′=n-C6H13, s-Bu, C6H11, and Ph) to afford corresponding amides and triphenylstibine oxide in fairly good yields. The amidation of RCO2H with R′NH2 was also catalyzed by the orgnoantimony compounds.

The diamines (Ia) - (Ie) are treated with CO2 (II) in the presence of triphenylstibine oxide, forming the cyclic ureas (III).

Irradiation of [Ru3(CO)12] in hexane in the presence of SbPh3gives the title complex as the major product. X-Ray diffraction has shown that the environment around the ruthenium atom is distorted trigonal bipyramidal in which the SbPh3occupies an equatorial site. The angle (C–Ru–C) between the equatorial carbonyl groups is 137° and that (C–Ru–C) between the axial carbonyl groups is 173°. This geometry represents an intermediate configuration in the dynamic rearrangement path between trigonal-bipyramidal and square-pyramidal co-ordination. The crystals are triclinic. The unit cell chosen has space group B1 with a= 14.02, b= 10.42, c= 17.49 A, α= 121.0, β= 89.2, γ= 81.7°, and Z= 4. The structure has been refined by least squares to R 0.036 for 4 157 counter amplitudes.

n/a

The chromatographic behaviour of some monosubstituted derivatives of the tetranuclear cluster (Cp)NiOs 3 (μH) 3 (CO) 9 (Cp = cyclopentadienyl) with group V donor ligands (benzonitrile tertiary phosphines, triphenylamine and triphenylstibine) is reported. In reversed-phase and adsorption liquid chromatography, the kind of the substituents strongly influences the retention volumes, the dimension of the whole cluster having less effect. Correlations of retention volumes with the nature of the substituents were found only for small of compounds.

Tetraphenylantimony 2-naphthalenesulfonate (I), tetraphenylantimony phenylmethanesulfonate (II), and bis(tetraphenylantimony) sulfate (III) were synthesized via reaction of pentaphenylantimony with 2-naphthalenesulfonic acid, triphenylantimony bis(phenylmethanesulfonate), and triphenylantimony sulfate, respectively, in toluene. Triphenylantimony bis(phenylmethanesulfonate) (IV) was synthesized from triphenylstibine, phenylmethanesulfonic acid, and hydrogen peroxide (taken in the molar ratio of 1 : 2 : 1). Organoantimony betaine \(Ph_3 \mathop {Sb}\limits^ + CH(Ph)SO_2 \bar O \left( V \right)\) (V) was obtained by reacting triphenylstibine with phenylmethanesulfonyl chloride in the presence of hydrogen peroxide. The structures of the compounds synthesized were determined using X-ray diffraction analysis. The Sb atoms in I–IV have distorted trigonal bipyramidal coordination. The Sb–C and Sb–O distances are equal to 2.100(4)–2.140(3) and 2.644(2) A in molecule I, 2.105(2)–2.131(2) and 2.699(1) A in II, 2.096(6)–2.169(6) and 2.101(6), 2.271(3) A in III, and 2.101(3)–2.102(5) and 2.111(2) A in IV. In V, the Sb atoms have close tetrahedral (2.105–2.115 A) and remote (2.65, 3.019 A) octahedral environment (the oxygen atoms of sulfo group of their own and neighboring molecules). Two betaine molecules are joined through the O atoms of the sulfo groups of bidentate phenylmethanesulfonate ligands to form a centrosymmetrical dimer. The intermolecular C(1)–H(1)···O(1) hydrogen bonds (3.10 A) are formed that strengthen the dimer.

Novel μ-oxo-bis(diphenylhydroxyantimony) di[2-(methylamino)ethoxide] (1) was obtained in the reaction of triphenylstibine oxide and 2-(methylamino)ethanol. Cyclic urethane derivatives were obtained by the reaction of 1 with CO2 or CS2 in good yields.

Submitted by Vitor Silverio Rodrigues (vitorsrodrigues@reitoria.unesp.br) on 2014-05-27T03:33:22Z No. of bitstreams: 0Bitstream added on 2014-05-27T14:38:12Z : No. of bitstreams: 1 2-s2.0-37049074710.pdf: 195727 bytes, checksum: e027959da8ade9c68b5b7212ad3e65b1 (MD5) Made available in DSpace on 2014-05-27T03:33:22Z (GMT). No. of bitstreams: 0 Previous issue date: 1987-12-01 The novel triphenylstibine complexes PtL2, PtL3, and (PtL3)nN2 (L = SbPh3) have been synthesised; the binary compounds are unusually unreactive even towards cold mineral acids. Departamento de Química Geral e Inorgânica Instituto de Química-UNESP Araraquara, S.P., CEP 14 800 Departamento de Química Geral e Inorgânica Instituto de Química-UNESP Araraquara, S.P., CEP 14 800

The reaction of benzamidine wiht S3N3Cl3 yields 1-chloro-3,5-diphenyl-1,2,4,6-thiatriazine, whose molecular structure has been determined by X-ray crystallography; reduction of Ph2C2N3SCl with triphenylantimony yields the radical species (Ph2C2N3S)· characterized by its e.s.r. spectrum.

Thiocyanato complexes of Ru(II) and Ru(III) with triphenylphosphine, triphenylarsine, triphenylstibine, pyridine and acetonitrile have been synthesized and characterised by analytical, spectral (UV and visible, IR) and cryoscopic data. Linkage isomerism of NCS − group is discussed.

The complexes [MX, (CO),L] (M = Mo and W; L = PPh, and AsPh,; X = C1 and Br) are currently under investigation as catalysts for the ring-opening polymerisation of norbornene, J and it is proposed that it is the ease of phosphine or arsine dissociation in these complexes which governs the rate determining step in the mechanism. Although a wide variety of bis-phosphine complexes of the type [MX, (CO),L] (M = Mo and W; X = C1, Br and I; L = phosphine) have been reported, hitherto no examples of “mixed” phosphine/phosphite complexes of this type have been prepared. In this communication we wish to report the synthesis of the new “mixed” sevencoordinate complexes [MI, (CO),L(P(OPh))] (M = Mo and W, L = PPh, AsPh, and SbPh).

1. Triethylamine demethylates 2-methylphenyl- and 2-dimethylsulfuranylidenedimedon to give, in the presence of sodium tetraphenylboranate, methyltriethylammonium tetraphenylboranate. 2. Triphenylstibine and triphenylbismuth demethylate 2-methylphenyl sulfur anylidenedimedon, which is indicated by the isolation of 2-phenylsulfenyldimedon in these reactions.

Irradiation of [Ru3(CO)12] in hexane in the presence of SbPh3gives the title complex as the major product. X-Ray diffraction has shown that the environment around the ruthenium atom is distorted trigonal bipyramidal in which the SbPh3occupies an equatorial site. The angle (C–Ru–C) between the equatorial carbonyl groups is 137° and that (C–Ru–C) between the axial carbonyl groups is 173°. This geometry represents an intermediate configuration in the dynamic rearrangement path between trigonal-bipyramidal and square-pyramidal co-ordination. The crystals are triclinic. The unit cell chosen has space group B1 with a= 14.02, b= 10.42, c= 17.49 A, α= 121.0, β= 89.2, γ= 81.7°, and Z= 4. The structure has been refined by least squares to R 0.036 for 4 157 counter amplitudes.

Conductometric titrations of PPh3Cl2 and AsPh3Cl2 with halogens and interhalogens show that the reactions are simple leading to the formation of adducts of types MPh3Cl2X2(M = P or As; X2= Br2, I2, ICl, or IBr) and MPh3Cl5I (M = P or As) in acetonitrile. The high molar conductances of the adducts suggest their formulation as MPh3Cl+ClX2– and MPh3Cl+ICl4– respectively. The polyhalide ions present have been identified from the u.v. spectra of the acetonitrile solutions. The reactions of MR3(M = P, As, or Sb) with ICl and ICl3 also give rise to highly conducting adducts in acetonitrile but the conductometric titration graphs indicate that these reactions are complex. Some of the adducts (PPh3Cl3I, AsPh3Cl3I, and AsPh3Cl5I) have been obtained as crystalline solids.

The thermodynamic characteristics of the complex between iodine and triphenylstibine oxide have been studied in dichloromethane by u.v. and i.r. spectroscopy and they are compared with other iodine–organic oxo-base complexes.

It has been shown for the first time that a lanthanide can be complexed by a stibine or a neutral arsine.

Simple, rapid and highly sensitive iodimetric amplification methods are described for the micro- and submicro-determination of antimony(III) in antibilharzial compounds. The methods are based on oxidation of the sample with an excess of periodate in acetate buffered medium, masking of the unreacted periodate with molybdate, and finally, iodimetric titration of the iodate that is released. Specific reactions have been found to occur for the four different compounds analysed owing to the presence, in the same molecule, of one or two antimony(III) and α-diol functions, both of which are oxidised quantitatively and simultaneously by periodate. Thus 3-, 9-, 15- and 18-fold amplification is achieved with triphenylstibine, tartar emetic, stibophen and diantimony piperazine tartrate, respectively. The total mean recovery is 99·49 per cent.

Twelve new complexes in the series RuHCl (η6-C6Me6)L [L = PBut2Me (5), PBut2Et (6), PBut2Pr (7), PMe3 (8), PMe2Ph (9), PMePh2 (10), PEtPh2 (ll), PPh2Pr (12), P( OPh )3, (13), P(OMe )3 (14), PEt3 (15), or PPh2(C6H4Me-o) (16)] have been prepared by one of three methods: 1, heating [RuCl2(η6-C6Me6)]2 with an excess of L and of anhydrous Na2CO3 in propan-2-ol (5)-(7); 2, heating pre-formed RuCl2(η6-C6Me6)L with an excess of Na2CO3 in propan-2-ol (8), (9), (11); 3, displacement of AsPh3 or SbPh3 by L from RuHCl (η6-C6Me6) L (L= AsPh3, SbPh3) (10)-(16). The new dihydrido complexes RuH2(η6-C6Me6)L (17)-(19) have been made by NaBH4 reduction of either RuCl2(η6C6Me6)L [L = PMe2Ph (17), PButMe2 (18) or of RuHCl (η6 -C6Me6)L [L = Pbut2Et (19)]. Under the conditions of method 2, RuCl2(η6-C6Me6)(PPh2(C6H4Me-o)) (4) undergoes deprotonation at the o- tolyl methyl group to give the cyclometallated complex RuCl (CH2C6H4PPh2-o)( η6-C6Me6) (20).

The triphenylstibine and dibenzyl sulphide complexes [Rh2(O2CMe)4(SbPh3)2] and [Rh2(O2CMe)4{S(CH2Ph)2}2] have been synthesised for the first time, and their electronic and Raman spectra recorded together with those of [Rh2(O2CMe)4(AsPh3)2]. The triphenylstibine complex was isolated as light brown crystals belonging to space group P, with one centrosymmetric molecule per unit cell. The structure has been refined to an R value of 0.027 for 3 608 observed intensities measured on a diffractometer. The triphenylarsine complex was isolated as maroon needles also belonging to space group P with one centrosymmetric molecule per unit cell. The structure has been refined to R 0.022 for 2 969 observed intensities. The dibenzyl sulphide complex crystallises as burgundy-coloured thin plates with two centrosymmetric molecules per unit cell, space group P21/c. The final R value was 0.056 for 2 469 observed intensities. The dirhodium tetra-acetate nuclei in the three complexes are essentially identical with each other and with the nuclei found in analogous bis adducts. The Rh–Rh bond lengths are 2.421 (4), 2.427(1), 2.406(3)A for the triphenylstibine, triphenylarsine, and dibenzyl sulphide complexes, respectively, and the Rh–Sb, Rh–As, and Rh–S bond lengths are 2.732(4), 2.576(1), and 2.561(5)A, respectively. The Rh–Sb distance is the longest (by 0.13 A) axial rhodium-to-donor-atom bond length known for a bis adduct of dirhodium tetra-acetate. The syntheses of these complexes further demonstrate the versatility of the dirhodium tetra-acetate nucleus in co-ordinating a wide variety of different axial ligands.

The complex compounds tris(triphenylarsine)- and tris(triphenylstibine)-chlororhodium(I)[RhCl(MPh3)3, M = As and Sb] have been prepared by interaction of MPh3 with bis(ethylene)chlororhodium(I). The complexes generally show behaviour similar to that previously described for tris(triphenylphosphine)chlororhodium(I). Although the present complexes are not as efficient as the phosphine complex as homogeneous hydrogenation catalysts for olefins, they undergo similar chemical reactions with hydrogen, ethylene, diphenylacetylene, tetrafluoroethylene, hydrogen chloride, and oxygen. The complexes obtained in these reactions have been studied by infrared and nuclear magnetic resonance spectroscopy.

Triarylphosphines react with thionyl chloride by oxygen transfer to give the triarylphosphine oxide and sulphur dichloride. Further reaction with sulphur dichloride gives the triarylphosphine dichloride and triarylphosphine sulphide and/or sulphur, depending on the phosphine and the mole ratio. Triphenylarsine and triphenylstibine react with thionyl chloride by chlorine transfer to give the dichloride, sulphur dioxide, and sulphur, or with sulphur dichloride to give the dichloride and sulphur. Further reaction of triphenylarsine (but not triphenylstibine) with sulphur gives triphenylarsine sulphide.

The dichlorides of triphenylarsine and triphenylstibine can be prepared in high yield, by the reaction in toluene solution at 0°, between triphenylarsine or triphenylstibine and sulphuryl chloride.

The unstable compounds dichlorotetracarbonyltungsten(II) and dibromo- tetracarbonyltungsten(II) have been prepared but not isolated in a pure state. The π-bonding ligands triphenylphosphine, triphenylarsine, and triphenylstibine have been used to prepare a series of moderately stable derivatives.

Diiodotetracarbonyls of molybdenum and tungsten(II) have been prepared for the first time by the direct interaction of the parent hexacarbonyls with iodine at room temperature under the influence of ultraviolet radiation. Reaction of the iodocarbonyls with donor ligands such as triphenylphosphine, triphenylarsine, and triphenylstibine generally gives neutral substitution products, but the reaction between the molybdenum compound and triphenylphosphine yielded the previously reported triphenylphosphonium salt of the triiodotricarbonyl(triphenylphosphine)-molybdate(II) ion. ��� Diiodotricarbonylbis(triphenylphosphine)tungsten(II) loses carbon monoxide on heating under vacuum to give the corresponding blue dicarbonyl compound. The dicarbonyl dissolved in dichloromethane readily absorbs carbon monoxide to reform the tricarbonyl and the compounds therefore represent a further carbon monoxide carrying system. ��

The conductance of methyl cyanide solutions of triphenyl-phosphine, -arsine, -stibine, and -bismuthine dihalides has been measured, and the molar conductance values are compared. Conductometric titrations of some triphenylphosphine–halogen systems indicate the formation of triphenylphosphine tetrahalides which are strong electrolytes and ionise as halogenotriphenylphosphonium trihalides like their triphenylarsine analogues. Each compound in the series Ph3PlnBr4 –n has been prepared. Tetrahalides of triphenylstibine and -bismuthine could not be prepared, although Ph3Sbl4 and Ph3Sbl3Br were indicated by conductometric titration.

Reaction of Pt(S2PPh2)2 with tertiary phosphines (PPh3, PMePh2, PMe2Ph) gives crystalline 1 : 1 and 1 : 2 adducts. With triphenylarsine or triphenylstibine, only 1 : 1 adducts can be isolated and with pyridine, i.r. evidence indicates that the 1 : 1 adduct is only stable in solution in the presence of an excess of pyridine. As reported earlier for the analogous palladium compounds, the 1 : 2 adducts rapidly dissociate to the 1 : 1 compounds in non-polar solvents (benzene or carbon disulphide); however, it is now found that they can be stabilised in more polar solvents (dichloromethane or nitromethane). Conductivity measurements in the latter suggests all these 1 : 2 adducts have a four-co-ordinate ionic structure and this is confirmed by an X-ray analysis of [Pd(S2PPh2)(PEt3)2]S2PPh2. An X-ray analysis on [Pd(S2PPh2)2(PPh3)] suggests a four-co-ordinate monomeric structure for the 1 : 1 compounds with uni- and bi-dentate co-ordination of dithioacid ligands. Finally, an empirical i.r. method for distinguishing unidentate, bidentate, and ionic modes of co-ordination of the diphenylphosphinodithioato-group to platinum and palladium is discussed.

Triphenylphosphine sulphide forms stable complexes with halides of PdII, PtII, PtIV, AuIII, AuI, and HgII. Triphenylphosphine selenide and triphenylarsine sulphide are generally similar but decompose with AuIII and PtIV, and triphenylstibine sulphide gives identifiable adducts only with copper(I) iodide and mercury(II) iodide. Ph3AsS extracts PtII from aqueous solution approximately seven times as fast as Ph3PSe, and sixteen times as fast as Ph3PS. The 1 : 1 adducts of HgCl2 with Ph3PS, Ph3PSe, and Ph3AsS are isomorphous with one another but not with dimeric (HgCl2,Ph3AsO)2. The P–S stretching frequency in Ph3PS falls by 40–50 cm.–1 on co-ordination, and the P–Se stretching frequency in Ph3PSe by about 20 cm.–1.