- Thermochemistry of Sulfur Atom Transfer. Enthalpies of Reaction of Phosphines with Sulfur, Selenium, and Tellurium, and of Desulfurization of Triphenylarsenic Sulfide, Triphenylantimony Sulfide, and Benzyl Trisulfide
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The enthalpies of reaction of neat PBu3 with solid sulfur (-27.1 ± 0.5 kcal/mol), selenium (-20.0 ± 0.6 kcal/ mol), and tellurium (-4.9 ± 0.6 kcal/mol) have been measured by solution calorimetry. The enthalpies of reaction of a series of phosphines with sulfur in toluene solution have been measured as follows (values in kcal/mol): PCy3 = -30.9 ± 1.9, PBu3 = -28.9 ± 0.3, PMe3 = -27.1 ± 0.4, PMe2Ph = -26.0 ± 0.5, PMePh2 = -23.8 ± 0.3. PPh3 = -21.5 ± 0.3. These values correlate with literature data for enthalpies of protonation and indicate that P to S σ donation is probably the dominant factor in determining the R3P=S bond strength, estimates for which range from 88 to 98 kcal/mol. The enthalpies of S atom transfer to PPh3 by S=AsPPh3 and S=SbPh3 in toluene solution are -17.7 ± 1.2 and -21.5 ± 1.0 kcal/mol, respectively. The enthalpy of removal of the central S atom from BzSSSBz by PCy3, yielding BzSSBz and S=PCy3, is -29.0 ± 1.8 kcal/mol. These data are used to establish a range of enthalpies of S atom transfer in these compounds which spans 31 kcal/mol from S=SbPPh3 to S=PCy3.
- Capps, Kenneth B.,Wixmerten, Bodo,Bauer, Andreas,Hoff, Carl D.
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- The thiol-based reduction of Bi(V) and Sb(V) anti-leishmanial complexes
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Low molecular weight thiols including trypanothione and glutathione play an important function in the cellular growth, maintenance and reduction of oxidative stress in Leishmania species. In particular, parasite specific trypanothione has been established as a prime target for new anti-leishmania drugs. Previous studies into the interaction of the front-line Sb(V) based anti-leishmanial drug meglumine antimoniate with glutathione, have demonstrated that a reduction pathway may be responsible for its effective and selective nature. The new suite of organometallic complexes, of general formula [MAr3(O2CR)2] (M = Sb or Bi) have been shown to have potential as new selective drug candidates. However, their behaviour towards the critical thiols glutathione and trypanothione is still largely unknown. Using NMR spectroscopy and mass spectrometry we have examined the interaction of the analogous Sb(V) and Bi(V) organometallic complexes, [SbPh3(O2CCH2(C6H4CH3))2] S1 and [BiPh3(O2CCH2(C6H4CH3))2] B1, with the trifluoroacetate (TFA) salt of trypanothione and L-glutathione. In the presence of trypanothione or glutathione at the clinically relevant pH of 4–5 for Leishmania amastigotes, both complexes undergo facile and rapid reduction, with no discernible difference. However, at a higher pH (6–7), the complexes behave quite differently towards glutathione. The Bi(V) complex is again reduced rapidly but the Sb(V) complex undergoes slow reduction over 8 h (t1/2 = 54 min.) These results give the first insights into why the highly oxidising Bi(V) complexes display low selectivity in their cytotoxicity towards leishmanial and mammalian cells, while the Sb(V) complexes show good selectivity.
- Duffin, Rebekah N.,Stephens, Liam J.,Blair, Victoria L.,Kedzierski, Lukasz,Andrews, Philip C.
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- Synthesis method of triphenyl antimony
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The invention discloses a synthesis method of triphenyl antimony, which comprises the following steps: adding higher fatty acid or higher fatty acid salt and adding sodium to organic solvent under theprotection of an inert gas, performing refluxing reaction and cooling to room temperature; slowly adding halogenated benzene into the obtained solution, then slowly dripping halogenated benzene solution of antimonous chloride, reaction under stirring, filtering the obtained reaction solution, evaporating organic solvent and halogenated benzene in the obtained filtrate under normal pressure to obtain a crude triphenyl antimony product; dissolving the crude product with petroleum ether, filtrating, concentrating the obtained filtrate and then freezing for crystallization to obtain triphenyl antimony. Triphenyl antimony is synthesized by the method disclosed by the invention, the utilization rate of raw materials is high, the use of high-pollution catalysts is avoided, the discharge of threewastes is reduced, production cost is reduced, the industrial application value is high, and the product has high purity and high yield.
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Paragraph 0061-0068; 0104-0109
(2018/11/03)
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- Pd-catalyzed P-arylation of triarylantimony dicarboxylates with dialkyl H-phosphites without a base: Synthesis of arylphosphonates
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The reaction of triarylantimony diacetates [Ar3Sb(OAc)2] with dialkyl H-phosphites [H-PO(OR)2] in the presence of a Pd(PPh3)4 (5 mol%) catalyst led to the formation of arylphosphonates in moderate to excellent yield under base-free conditions. This reaction is the first example of carbon-phosphorus bond formation by using an organoantimony compound as a pseudo-halide.
- Matsumura, Mio,Dong, Yuqiang,Kakusawa, Naoki,Yasuike, Shuji
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p. 130 - 133
(2015/02/19)
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- Establishing the coordination chemistry of antimony(v) Cations: Systematic assessment of Ph4Sb(OTf) and Ph3Sb(OTf)2 as Lewis acceptors
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The coordination chemistry of the stiboranes Ph4Sb(OTf) (1 a, OTf = OSO2CF3) and Ph3Sb(OTf)2 (3) with Lewis bases has been investigated. The significant steric encumbrance of the Sb center in 1 a precludes interaction with most ligands, but the relatively low steric demands of 4-methylpyridine-N-oxide (OPyrMe) and OPMe3 enabled the characterization of [Ph4Sb(OPyrMe)][OTf] (2 a) and [Ph4Sb(OPMe3)][OTf] (2 b), rare examples of structurally characterized complexes of stibonium acceptors. In contrast, 3 was found to engage a variety of Lewis bases, forming stable isolable complexes of the form [Ph3Sb(donor)2][OTf]2 [donor=OPMe3 (6 a), OPCy3 (6 b, Cy=cyclohexyl), OPPh3 (6 c), OPyrMe (6 d)], [Ph3Sb(dmap)2(OTf)][OTf] (6 e, dmap=4-(dimethylamino)pyridine) and [Ph3Sb(donor)(OTf)][OTf] [donor=1,10-phenanthroline (7 a) or 2,2′-bipy (7 b, bipy=bipyridine)]. These compounds exhibit significant structural diversity in the solid-state, and undergo ligand exchange reactions in line with their assignment as coordination complexes. Compound 3 did not form stable complexes with phosphine donors, with reactions instead leading to redox processes yielding SbPh3 and products of phosphine oxidation.
- Robertson, Alasdair P. M.,Chitnis, Saurabh S.,Jenkins, Hilary A.,McDonald, Robert,Ferguson, Michael J.,Burford, Neil
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p. 7902 - 7913
(2015/05/20)
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- Simple base-free Miyaura-type borylation of triarylantimony diacetates with tetra(alkoxo)diborons under aerobic conditions
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The reaction of triarylantimony diacetates with tetra(alkoxo)diborons in the presence of PdCl2(PPh3)2 (1 mol%) catalyst resulted in the Miyaura-type B-arylation to form arylboronates in moderate to good yields under base-free conditions. In the present reaction, two of the three aryl groups of antimony reagent were transferred to the coupling products when the reaction was carried out under aerobic conditions, although only one of the three aryl group of the antimony reagent was involved under an argon atmosphere. The broad scope of the reaction was demonstrated by using a variety of triarylantimony diacetates with sterically hindered aryl groups and highly reactive p-bromo-functionalized aryl derivatives.
- Yasuike, Shuji,Dong, Yuqiang,Kakusawa, Naoki,Matsumura, Mio,Kurita, Jyoji
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- Coordination complexes of Ph3Sb2+ and Ph 3Bi2+: Beyond pnictonium cations
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The syntheses of salts containing ligand-stabilized Ph3Sb 2+ and Ph3Bi2+ dications have been realized by in situ formation of Ph3Pn(OTf)2 (Pn=Sb or Bi) and subsequent reaction with OPPh3, dmap and bipy. The solid-state structures demonstrate diversity imposed by the steric demands and nature of the ligands. The synthetic method has the potential for broad application enabling widespread development of the coordination chemistry for PnV acceptors. A coordinated effort: The synthesis and characterization of OPPh 3, dmap (4-(dimethylamino)pyridine), and bipy (2,2′-bipyridine) complexes of SbV and BiV are reported. The solid-state structures demonstrate structural diversity driven by the steric demands and the nature of the ligands.
- Robertson, Alasdair P. M.,Burford, Neil,McDonald, Robert,Ferguson, Michael J.
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supporting information
p. 3480 - 3483
(2014/04/03)
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- Reactions of bis(tri- tert -butylphosphine)platinum with metal hydride complexes. the reactions of Pt(P-t-Bu3)2 with HRe(CO) 4SbPh3
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Pt(P-t-Bu3)2 reacts with the rhenium hydride complex HRe(CO)4(SbPh3), 1, at 25 °C to give the complex PtRe(CO)4(Ph)(P-t-Bu3)(μ-SbPh2)(μ-H), 2, in 75% yield by the oxidative-addition of a Sb-C bond on the SbPh3 ligand of 1 to a Pt(P-t-Bu3) group generated by loss of a P-t-Bu 3 ligand from Pt(P-t-Bu3)2. Compound 2 contains a Pt-Re bond [Pt(1)-Re(1) = 3.0971(7) A] with a bridging SbPh2 ligand and a bridging hydrido ligand. At 98 °C, Pt(P-t-Bu3) 2 reacts with two equivalents of 1 to yield the compounds PtRe 2(CO)8[PH(t-Bu2)](Ph)(μ-SbPh 2)2(μ-H), 3, PtRe2(CO)8(SbPh 3)(Ph)(μ-SbPh2)2(μ-H), 4, and PtRe 2(P-t-Bu3)(μ-SbPh2)2(μ-SbPh), 5. Compounds 3 and 4 both contain five-membered Re2Sb2Pt rings formed from two mutually bonded Re(CO)4 groups and two bridging SbPh2 ligands that are both bonded to the Pt atom. Compound 4 was obtained from 2 independently by reaction with 1. Pt(P-t-Bu3) 2 reacts with 1 at 68 °C under a hydrogen atmosphere to yield 2, 4, and the new compound, HPtRe2(CO)8(P-t-Bu 3)(μ-SbPh2)2(μ-H), 6, which also contains a five-membered Re2Sb2Pt ring similar to those found in 3 and 4. Five compounds were obtained in low yields when 2 was thermally decomposed under nitrogen at 100 °C: 5 (4%); Re2(CO) 8(μ-SbPh2)2, 7 (6% yield); RePh(CO) 4SbPh3, 10 (4%); Re2(CO)8[PtH(CO)(P- t-Bu3)](μ3-SbPh)(μ-SbPh2), 11 (4%); RePh(CO)4[PtH(CO)P(t-Bu)3](μ-SbPh2), 12 (7%). Of these, only 12 is new. Compound 12 is a CO adduct of 2 and was obtained independently by the addition of CO to 2. The CO ligand was added to the platinum atom, the Pt-Re bond of 2 was cleaved, and the phenyl group was shifted to the rhenium atom. The two metal atoms are linked solely by the bridging SbPh2 ligand. Seven compounds, 5 (9% yield), 7 (26%), Pt 3(CO)3(P-t-Bu3)3, 9 (71%), 11 (7%), 12 (8%), PtRe2(CO)9P(t-Bu)3(μ-H) 2, 13 (13%), and Re3(CO)13(μ3- SbPh)(μ-SbPh2), 14 (18%), were obtained when 2 was allowed to react with CO at room temperature. Of these, only compound 14 is new. Compound 14 contains no platinum atoms. The structure of 14 contains two Re(CO) 4 groups linked by a bridging SbPh2 ligand and a bridging SbPh ligand. The bridging SbPh ligand also contains a pendant Re(CO)5 group.
- Adams, Richard D.,Pearl Jr., William C.
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p. 3887 - 3895
(2011/01/05)
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- Oxidation of triphenylantimony with 4-hydroperoxy-2-hydroxy-3,4,6- triisopropylcyclohexa-2,5-dienone or 3,4,6-triisopropyl-1,2-benzoquinone
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According to the NMR spectroscopic data, the oxidation of triphenylantimony with 4-hydroperoxy-2-hydroxy-3,4,6-triisopropylcyclohexa-2,5-dienone involves three steps. The first step affords the 2,4,10,12-tetraoxa-3,11- distibatricyclo[11.3.1.15,9]octadecatetraene derivative. The latter is rearranged into benzodioxastibolone derivatives followed by the rearrangement into 4,6,7-triisopropyl-2,2,2-triphenyl-1,3,2-benzodioxastibol-5-ol. The transformation of the latter depends on the presence of oxygen and the mode of its dosing.
- Abakumov,Vavilina,Kurskii,Abakumova,Fukin,Cherkasov,Shavyrin,Baranov
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p. 1813 - 1820
(2008/09/19)
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- Zinc reaction with diphenylantimony and diphenylbismuth chlorides in aprotic solvents
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Products of zinc oxidation with diphenylantimony and diphenylbismuth chlorides in aprotic solvents are established. The effective adsorption constants of the reagents on the metal surface and the rate constants and activation energies of the processes und
- Losev,Klement'eva,Maslennikov,Spirina
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p. 1581 - 1583
(2008/02/07)
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- Oxidation of magnesium with diphenylbismuth and diphenylantimony chlorides in polar solvents
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The intermediate and final products of the reactions of magnesium with diphenylantimony and diphenylbismuth chlorides were identified, and the formal kinetic relationships of the process were elucidated. The apparent equilibrium constants, enthalpies, and
- Maslennikov,Klement'eva,Losev, Ya. V.,Spirina,Maslennikov
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- Reaction of bis(phenylethynyl)itterbium with tetraphenylantimony halides
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Phenylethynyl itterbium derivative (PhC≡C)2Yb(THF) 2 reacts with tetraphenylantimony halides in tetrahydrofuran (THF) at room temperature to form triphenylantimony, phenylacetylene, benzene, and phenylethynylitterbium PhC≡CYbX(THF)4 and itterbium YbX 2(THF)4 halides; X = Cl, Br, I. The reduction of the antimony derivative is accompanied with the generation of phenyl and phenylethynyl radicals. Pleiades Publishing, Inc., 2006.
- Zhiltsov,Pimenova,Gushchin,Morgunova
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p. 705 - 707
(2008/02/02)
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- Catalytic C-phenylation of methyl acrylate with tetraphenylantimony(v) halides and carboxylates
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Catalytic C-phenylation of methyl acrylate to methyl cinnamate with the Ph4SbX complexes (X = F, Cl, Br, OH, OAc, O2CEt) in the presence of the palladium compounds PdCl2, Pd(OAc)2, Pd2(dba)3, Pd(Ph3P)2Cl2, and Pd(dppf)Cl2 (dba is dibenzylideneacetone and dppf is bis(diphenylphosphinoferrocene)) was studied in organic solvents (MeCN, THF, DMF, MeOH, and AcOH). The highest yield of methyl cinnamate (73% based on the starting organometallic compound) was obtained for the Ph4SbCl- PdCl2 (1:0.04) system in acetonitrile.
- Gushchin,Grunova,Moiseev,Morozov,Shavyrin,Dodonov
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p. 1376 - 1379
(2007/10/03)
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- Oxidizing ability of a series of (Tropon-2-ylimino)pnictoranes (Pnictogen = P, As, Sb, and Bi) toward some alcohols
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In order to gain a better understanding of the oxidizing ability of a series of (tropon-2-ylimino)pnictoranes of the general structure Ph3M=NR (R = tropon-2-yl; M = P, As, Sb, and Bi), reactions were run with some alcohols such as benzopinacol (1,1,2,2-tetraphenyl-1,2-ethanediol), benzoin, cinnamyl alcohol, 1-phenylethanol, a mixture of cis- and trans-4-t-butylcyclohexanol, 2-phenylethanol, and 1-phenyl-1,3-propandiol. Iminophosphorane oxidized only benzopinacol to give benzophenone, while both arsorane and stiborane oxidized benzopinacol and benzoin to give benzophenone and benzil, respectively. On the other hand, iminobismuthorane has appreciable oxidizing ability, and reacted with the alcohols mentioned above, except the primary alcohol, to give the corresponding carbonyl compounds. Iminobismuthorane reacted with 1-phenyl-1,3-propandiol selectively to oxidize benzyl alcohol moiety, but not a primary alcohol moiety, to give 3-hydroxy-1-phenyl-1-propanone. Thus, the oxidizing ability of a series of (tropon-2-ylimino)pnictoranes is demonstrated to be in the order of iminophosphorane 3M+--NR canonical structure) and electrophilic character of pnictogen elements of a series of iminopnictoranes appear to increase their oxidizing ability when the pnictogen stands lower in the periodic table.
- Mitsumoto, Yuhki,Nitta, Makoto
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p. 1029 - 1034
(2007/10/03)
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- Synthesis and structure of tetraphenylantimony N,N-diethyldithiocarbamate
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Tetraphenylantimony chloride was reacted with sodium N,N-diethyldithiocarbamate in water to obtain tetraphenylantimony N,N-diethyldithiocarbamate in 98% yield. According to X-ray diffraction data, the configuration of the molecule of tetraphenylantimony diethyldithiocarbamate is distorted octahedron, and the Sb-S bond lengths are 2.705(2) and 2.771(2) A.
- Sharutin,Sharutina,Platonova,Pakusina,Krivolapov,Gubaidullin,Litvinov
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p. 1379 - 1382
(2007/10/03)
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- Aroxytetraaryl antimony compounds. Synthesis, structure, and thermolysis
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The reactions of pentaphenylantimony with 3,5-di-tert-butylphenol and of penta-p-tolylantimony with 4,6-dibromo-2-methylphenol in toluene at 20°C were used to prepare Ph4SbOC6H3(t-Bu)2-3,5 and p-Tol4SbOC6H2Me-2,Br2-4,6, respectively. The structures of the products were established by X-ray diffraction analysis. The Sb atoms in the molecules have trigonal-bipyramidal coordination with an axial aroxy group. The Sb-O and C-O were found to depend on the nature of substituent in the aroxy group, and an explanation of this phenomenon was proposed. Thermolysis of (3,5-di-tert-butylphenoxy)tetraphenylantimony at 220°C (1 h) results in quantitative formation of aryl phenyl ether and triphenylstibine. Thermolysis of (2,6-dimethyl-phenoxy)tetraphenylantimony yields triphenylstibine and 2,2′,6,6′-tetramethyldiphenoquinone.
- Sharutin,Sharutina,Osipov,Vorob'eva,Muslin,Bel'skii
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p. 867 - 872
(2007/10/03)
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- Reactions of organolanthanide compounds RLnI (Ln = Yb, Eu, Sm) with organic derivatives of silicon, tin, lead, and antimony
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Reactions of compounds RLnI (R = Alk, Ar; Ln = Yb, Eu, Sm) with hexaalkyl(aryl)-distannanes, trimethylsilyltriphenyltin, and lead and antimony acetates were studied. The reactions with Sn-Sn and Si-Sn organic derivatives result in cleavage of Sn-Sn amd Sn-Si bonds with formation of tetrasubstituted stannanes and reactive organometallic derivatives with an Sn-Ln or Si-Ln bond. The reactions of RYbI with lead and antimony acetates and with tetraethoxysilane cause cleavage of the Pb-O, Sb-O, or Si-O bond with formation of tetrasubstituted derivatives of lead and silicon or trisubstituted antimony derivatives.
- Rybakova,Syutkina,Petrov
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p. 244 - 246
(2007/10/03)
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- Synthesis and structure of triphenylantimony Bis(2,4-dimethylbenzenesulfonate)
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Triphenylstibine was reacted with 2,4-dimethylbenzenesulfonic acid in toluene in the presence of air oxygen to obtain triphenylantimony bis(2,4-dimethylbenzenesulfonate). By X-ray diffraction data, the antimony atom in the complex has trigonal-bipyramidal configuration with axial 2,4-dimethylbenzenesulfonate oxygens. The Sb-O and Sb-C bond lengths are 2.105(2), 2.133(2), and 2.101(4), 2.078(5), and 2.094(5) A, and the CSbC and OSbO bond angles are 127.1(2), 113.5(2), 119.3(2), and 176.8(1)°, respectively.
- Sharutin
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p. 1569 - 1572
(2007/10/03)
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- Reaktionen von Ph2SbH und p-TolSbH2 mit organischen Verbindungen
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p-TolSbH2 reacts with styrene with formation of ethylbenzene and (p-TolSb)n (n=4, 5 in benzene). The action of phenyl acetylene on p-TolSbH2 gives styrene. Addition of Ph2SbH on phenyl acetylene in the presence of AIBN (azodiisobutyronitrile) yields 95% trans- and 5% cis-PhCH=CHSbPh2. Ph2SbH reacts with benzaldehyde in the presence of AIBN with formation of benzylalcohol (98%) and with various prochiral ketones in the presence of chiral auxiliares to give alcohols in high optical yields. Benzotrichloride reacts with Ph2SbH in the presence of PdCl2 to give benzylidene chloride. 1-Bromo adamantane, dibromo cholestanol, 2-chloro acetophenone, cinnamic acid chloride, and chloro acetophenone react with Ph2SbH/AIBN with substitution of the halogen atoms by hydrogen. Benzylbenzoate is formed the by action of Ph2SbH/AIBN on benzoyl chloride.
- Breunig,Probst
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p. 297 - 303
(2007/10/03)
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- Two-step synthesis of triarylmetals (As, Sb, Bi) starting from the metal oxides and 2,6-dimethoxybenzenethiol
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Reported here is a new synthetic method of triarylmetals MAr3 (M = As, Sb, Bi). It is composed of two-step reactions starting from the metal oxides: (1) A reaction of the metal oxide with 2,6-dimethoxybenzenethiol ΦSH [Φ = 2,6-(MeO)2C6H3] in the presence of acid to give the thiolatometals M(SΦ)3, and (2) A reaction of M(SΦ)3 with organolithium reagent LiAr to give MAr3 (Ar = Ph, 4-MeC6H4, 4-Me2NC6H4, Φ). Since ΦSH is odorless and crystalline, most of it can be recovered after the reactions without difficulty for repeated usages. The intermediates M(SΦ)3 are also crystalline and inert against hydrolysis.
- Wada, Masanori,Natsume, Satoko,Suzuki, Shinobu,Uo, Akira,Nakamura, Michiaki,Hayase, Shuichi,Erabi, Tatsuo
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p. 223 - 227
(2007/10/03)
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- Reactions of Pentaarylantimony with ortho-Substituted Phenols
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Pentaarylantimony was reacted with ortho-substituted phenols at ～20°C to obtain a series of aroxytetraphenylantimonies Ar4SbOAr′. An X-ray diffraction analysis of the synthesized compounds was performed.
- Sharutin,Sharutina,Osipov,Pushilin,Muslin,Lyapina,Zhidkov,Bel'skii
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p. 1435 - 1437
(2007/10/03)
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- Thermal Decomposition of Some Dioxastibolanes
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Thermal decomposition of λ**5-dioxastibolanes Ph3SbO2R obtained from triphenylantimony and primary, secondary, and tertiary 1,2-diols is accompanied by cleavage of the endocyclic C-C bond, oxidation of the aliphatic moiety, and liberation of triphenylantimony. When the group R contains a hydrogen atom at the α-carbon atom, decomposition of the organometallic compound involves the triphenylantimony fragment, the C-C bond being retained.
- Zaburdyaeva, S. N.,Fedorov, A. Yu.,Dodonov, V. A.
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p. 721 - 723
(2008/10/08)
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- Electrochemical studies on organometallic compounds XXXVI. New aspects of the electroreduction of (Ph2Sb)2O, (Ph2Sb)2, Ph2Sb(nBu), and Ph3Sb
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Electroreduction of (Ph2Sb)2O (1) in THF gives Ph2Sb-, which can also be obtained by uptake of two electrons on (Ph2Sb)2 (2).Ph2Sb- reacts with the supporting salt (nBu4NPF6) to yield tributylamine and Ph2Sb(nBu) (3).The electroreduction of 3 and Ph3Sb (4) gives also the anion Ph2Sb-.There is a considerable influence of the electrode surface on the redox properties of 1-4.Mechanistic aspects are discussed.
- Mourad, Y.,Mugnier, Y.,Breunig, H.J.,Ates, M.
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- NEUE DARSTELLUNG, SCHWEFELINSERTION UND HYDROLYSE DER PHENYL(TRIMETHYLSILYL)STIBANE
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Reaction of Mg and Me3SiCl with Ph2SbCl or PhSbCl2 gives Ph2SbSiMe3 (1) or PhSb(SiMe3)2 (2).Sulfur inserts into 1 to give Ph2SbSSiMe3 (3).Products of action of S8 on 2 are 3, PhSb(SSiMe3)2 (4), (Me3Si)2S, and Sb2S3.Hydrolysis or methanolysis of 1, or 2 give Ph2SbH (5), or PhSbH2 (6), respectively.Key words: Diphenyl(trimethylsilyl)stibane; phenylbis(trimethylsilyl)stibane; diphenyl(trimethylsilyl-thio)stibane; diphenylstibane; phenylstibane.
- Ates, M.,Breunig, H. J.,Guelec, S.
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p. 129 - 134
(2007/10/02)
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- Phosphine-substituted and phosphido-bridged metal clusters in homogeneous catalysis I. Synthesis and reactivity of (η5-C5H5)NiM3(μ-H)3(CO)(9-n)Ln (M = Ru, Os, n = 1,2: L = PPh3, PPh2H, PCy3, PEt3) and M3(CO)(12-n)Ln (M = Ru, N = 1-3: L = PPh3,
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The complexes (η5-C5H5)NiM3(μ-H)3(CO)(9-n)Ln (M = Ru, Os, n = 1.2: L = PPh3, PPh2H, PCy3, PEt3) and M3(CO)(12-n)Ln (M = Ru, n = 1-3: L = PPh3, PPh2H, PCy3, PEt3; M = Os, n = 1,2: L = PPh3) have been synthesized by new or known procedures.Reacti
- Castiglioni, Mario,Giordano, Roberto,Sappa, Enrico
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- Phenylantimony Bis(monothioacetate); Its Preparation, Structure and Stability
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Phenylantimony bis(monothioacetate) has been prepared and fully characterised by single crystal X-ray diffraction.The crysatals are triclinic, P1, with a 10.761(4), b 7.304(3), c 9.608(7) Angstroem, α 112.84(5), β 102.57(5) and γ 100.17(5) grad.The thioacetate groups bond primarily via sulphur (Sb-S 2.451, 2471 Angstroem) but substantial Sb...O interactions lead to a bis-chelate structure.Isolated PhSb(SAc)2 molecules have distorted square-pyramidal geometry with an apical phenyl group but intermolecular Sb...S interactions (3.802 Angstroem) trans to the phenyl group give weak dimers in the solid state.Attempts to prepare Ph2SbSAc gave only mixtures PhSb(SAc)2 and Ph3Sb; in the related acetate series, Ph2SbOAc is well-known, but PhSb(OAc)2 could not be prepared.Possible reasons for the instability of Ph2SbSAc and PhSb(OAc)2 are considered.
- Hall, M.,Sowerby, D. B.,Falshaw, C. P.
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p. 321 - 328
(2007/10/02)
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- Mechanism of the oxidation of triphenyl derivatives of P, As, and Sb by peroxodiphosphate
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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.
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p. 2285 - 2289
(2007/10/02)
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- ONE POT SYNTHESIS FROM THE ELEMENTS OF SYMMETRICAL AND UNSYMMETRICAL TRIARYL-PHOSPINES, -ARSINES AND -STIBINES BY THE SRN1 MECHANISM
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The reactions of elemental phosphorus, arsenic and antimony with sodium metal in liquid ammonia form "M-3" species that react with haloarenes under irradiation to form symmetrical triaryl derivatives of these metals by the SRN1 mechanism in fair to good yields.Further reaction with sodium metal gives a derivative nucleophile (diarylphosphide and diarylarsenide ions) that reacts with another haloarene under irradiation to form unsymmetrical phosphines and arsines.
- Bornancini, Esteban R.,Alonso, Ruben A.,Rossi, Roberto A.
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p. 177 - 184
(2007/10/02)
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- THE REACTION OF TETRACHLORO-o-BENZOQUINONE WITH THE SULFIDES OF TRIPHENYLARSINE AND TRIPHENYLSTIBINE
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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.
- Sidky, M. M.,Mahran, M. R.,Abdou, W. M.
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p. 129 - 136
(2007/10/02)
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- New Reagents, XXV. lithium and -copper(I); Synthesis and Preparative Applications
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lithium (1b), quantitatively obtained by organoelement-lithium exchange from bis(diphenylstibino)methane (1a), reacts with aldehydes and ketones to give (β-hydroxyalkyl)diphenylstibanes (2) (39 - 82percent).These compounds are now well accessible. copper(I) (5), quantitatively obtained by transmetalation from 1b, reacts with alkyl iodides to give alkyldiphenylstibanes (3) (45 - 80percent). (Diphenylphosphino)- (4a) and (diphenylarsino)(diphenylstibino)methane (4b) were obtained from 1b in unsatisfactory yields only.
- Kauffmann, Thomas,Joussen, Rolf,Klas, Norbert,Vahrenhorst, Annemarie
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p. 473 - 478
(2007/10/02)
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- Reduction of Butyl- and Phenylantimony(III) Bromides and of t-Butylantimony(III) Chlorides with Magnesium in the Presence of Trimethylchlorosilane: Competition of Sb-Sb and Sb-Si Coupling
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Butylantimony(III) bromides react with Mg in tetrahydrofuran (THF) even in presence of Me3SiCl exclusively with Sb-Sb-coupling: Starting from Bu2SbBr, Bu2SbSbBu2 is formed and BuSbBr2 is reduced to (BuSb)x.Sb-Si-coupling dominates in the reactions of Ph2SbBr or t-Bu2SbCl with Mg/Me3SiCl/THF yielding Ph2SbSiMe3 or t-Bu2SbSiMe3.Both Sb-Sb- and Sb-Si-coupling reactions are observed, when PhSbBr2 reacts with Mg and Me3SiCl yielding PhSb(SiMe3)2 and (PhSb)x.The same reactants can also form the distibanes Ph2(SiMe3)2Sb2 and PhSb(SiMe3)3Sb2.The reaction of t-BuSbCl2 with Mg/Me3SiCl yields the stibines t-BuSb(SiMe3)2 and Sb(SiMe3)3 together with (t-BuSb)4.In the reactions of t-BuSbCl2 or PhSbBr2 the ratio of Sb-Sb- and Sb-Si-coupling can be strongly influenced by using different reaction conditions. - Keywords: Diphenyl(trimethylsilyl)stibine, Phenylbis(trimethylsilyl)stibine, Di-tert-butyl(trimethylsilyl)stibine, tert-Butyl-bis(trimethylsilyl)stibine
- Breunig, Hans Joachim,Severengiz, Tevfik
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p. 395 - 400
(2007/10/02)
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- ANTIMONY-SULPHUR BONDED COMPOUNDS. IV. FURTHER STUDIES ON THE THERMAL DECOMPOSITION OF TETRA-ORGANOANTIMONY MERCAPTIDES
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The thermolytic decompositions of Ph4SbSAr in organic solvents are reported.Solvent-derived products from decompositions in CCl4 and cyclohexane confirm the free radical nature of the reactions.Thermal decompositions of Ph3(p-MeC6H4)SbSC6H4OMe-p, or Ph(p-
- Bedi, Bhupinder S.,Grant, Douglas W.,Tewnion, Lesley,Wardell, James L.
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p. 251 - 266
(2007/10/02)
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- NUCLEOPHILIC SUBSTITUTION REACTIONS ON ANTIMONY(III) 0,0-DISUBSTITUTED PHOSPHORODITHIOATES
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Antimony(III) tris(O,O-diisobutyl phosphorodithioate), 1 (R=i-Bu) has been found to undergo a nucleophilic displacement reaction with sodium 1-propanethiolate to give antimony(III) tris-(1-propanethiolate), 4, and sodium O,O-diisobutyl phosphorodithioate (8, R=i-Bu).Reaction of 1 (R=i-Bu) with phenyllithium gave triphenylstibine and lithium O,O-diisobutyl phosphorodithioate.Similar reactions of various compounds of type 1 with the sodium salts of carboxylic acids and with the sodium salt of pyrrole were also found to occur.Furthermore, antimony tris(O,O-diisobutyl phosphorodithioate), 1 (R=i-Bu), was found to undergo solvolysis with n- propyl mercaptan to give 4 and O,O-diisobutyl phosphorodithioic acid 5.Compounds of type 1 are used as passivating agents in petroleum refining, and reactions of the types described for 1 with n-propyl mercaptan and with the salts of carboxylic acids probably occur when "Phil-Ad CA" is added to the feedstock of a fluid catalytic cracking unit.
- McEwen, W. E.,Woo, E. J.,Kalbacher, B. J.
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- Synthesis and Spectral Studies of Triphenylantimony(V) Oximates and Benzamidoximate
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Complexes of the general formula, Ph3Sb(ONCRR')2 (where R and R'=Me,Me; Me,Et; Me,Pr; Me,Ph; Et,Et; Et,Pr and NH2,Ph), have been synthesised and characterised.A trigonal bipyramidal geometry has been suggested for these complexes.They can be purified by recrystallization and on distillation under reduced pressure, they yield triphenylantimony.
- Jain, V. K.,Bohra, R.,Mehrotra, R. C.
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p. 408 - 410
(2007/10/02)
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- TETRAPHENYLANTIMONY MERCAPTIDES, Ph4SbSAr: THERMAL DECOMPOSITION
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The products of the thermal decomposition of Ph4SbSC6H4X (X = H, p-Me, p-OMe, o-OMe and p-Br) include XC6H4SPh, (XC6H4S)2, Ph3Sb, Ph2 and PhH.Evidence is presented to show that at least a major part of the reaction occurs via free radicals.
- Wardell, James L.,Grant, Douglas W.
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p. 345 - 352
(2007/10/02)
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- Selective formation of ethanol from methanol, hydrogen and carbon monoxide
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A process for the selective formation of ethanol which comprises contacting methanol, hydrogen and carbon monoxide with a catalyst system comprising cobalt acetylacetonate, a tertiary organo Group V A compound of the periodic Table, a first promoter comprising an iodine compound and a second promoter comprising a ruthenium compound.
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- Aqueous electrochemistry of quaternary organoantimony ions
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The series of quaternary organoantimony ions, (CH3)m(C6H5)m-4Sb + (m = 1-4), has been studied in aqueous solution using dc polarography, cyclic voltammetry, and controlled potential electrolysis. Tetramethylantimony ion undergoes a single two-electron reduction to trimethylantimony and methane. The other three ions in the series are reduced in two one-electron steps. The first electron transfer involves the formation of an antimony(IV) species which rapidly reacts with the electrode metal to form an organomercury radical and a trivalent organoantimony compound. The organomercury radical disproportionates to form a diorganomercury compound. The second electron transfer gives trivalent organoantimony compounds and hydrocarbons. In two of the three possible cases both methyl and phenyl groups are lost by the antimony. The relative losses are different following the first and second electron transfer. Two factors govern the loss of the hydrocarbon group: the stability of the resulting hydrocarbon radical or carbanion and the stability of the resulting antimony compounds.
- Kok, Gregory L.,Morris, Michael D.
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p. 2146 - 2150
(2008/10/08)
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