603-36-1Relevant articles and documents
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
Capps, Kenneth B.,Wixmerten, Bodo,Bauer, Andreas,Hoff, Carl D.
, p. 2861 - 2864 (1998)
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.
The thiol-based reduction of Bi(V) and Sb(V) anti-leishmanial complexes
Duffin, Rebekah N.,Stephens, Liam J.,Blair, Victoria L.,Kedzierski, Lukasz,Andrews, Philip C.
, (2021/05/10)
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.
Synthesis method of triphenyl antimony
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Paragraph 0061-0068; 0104-0109, (2018/11/03)
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.
Pd-catalyzed P-arylation of triarylantimony dicarboxylates with dialkyl H-phosphites without a base: Synthesis of arylphosphonates
Matsumura, Mio,Dong, Yuqiang,Kakusawa, Naoki,Yasuike, Shuji
, p. 130 - 133 (2015/02/19)
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.
Establishing the coordination chemistry of antimony(v) Cations: Systematic assessment of Ph4Sb(OTf) and Ph3Sb(OTf)2 as Lewis acceptors
Robertson, Alasdair P. M.,Chitnis, Saurabh S.,Jenkins, Hilary A.,McDonald, Robert,Ferguson, Michael J.,Burford, Neil
, p. 7902 - 7913 (2015/05/20)
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.
Simple base-free Miyaura-type borylation of triarylantimony diacetates with tetra(alkoxo)diborons under aerobic conditions
Yasuike, Shuji,Dong, Yuqiang,Kakusawa, Naoki,Matsumura, Mio,Kurita, Jyoji
, p. 80 - 85 (2014/06/24)
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.
Coordination complexes of Ph3Sb2+ and Ph 3Bi2+: Beyond pnictonium cations
Robertson, Alasdair P. M.,Burford, Neil,McDonald, Robert,Ferguson, Michael J.
supporting information, p. 3480 - 3483 (2014/04/03)
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.
Reactions of bis(tri- tert -butylphosphine)platinum with metal hydride complexes. the reactions of Pt(P-t-Bu3)2 with HRe(CO) 4SbPh3
Adams, Richard D.,Pearl Jr., William C.
, p. 3887 - 3895 (2011/01/05)
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.
Oxidation of triphenylantimony with 4-hydroperoxy-2-hydroxy-3,4,6- triisopropylcyclohexa-2,5-dienone or 3,4,6-triisopropyl-1,2-benzoquinone
Abakumov,Vavilina,Kurskii,Abakumova,Fukin,Cherkasov,Shavyrin,Baranov
, p. 1813 - 1820 (2008/09/19)
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.
Reaction of bis(phenylethynyl)itterbium with tetraphenylantimony halides
Zhiltsov,Pimenova,Gushchin,Morgunova
, p. 705 - 707 (2008/02/02)
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.
