- Structural, spectroscopic and computational examination of the dative interaction in constrained phosphine-stibines and phosphine-stiboranes
-
Abstract A series of phosphine-stibine and phosphine-stiborane peri-substituted acenaphthenes containing all permutations of pentavalent groups -SbClnPh4-n (5-9), as well as trivalent groups -SbCl2, -Sb(R)Cl, and -SbPh2 (2-4, R=Ph, Mes), were synthesised and fully characterised by single crystal diffraction and multinuclear NMR spectroscopy. In addition, the bonding in these species was studied by DFT computational methods. The P-Sb dative interactions in both series range from strongly bonding to non-bonding as the Lewis acidity of the Sb acceptor is decreased. In the pentavalent antimony series, a significant change in the P-Sb distance is observed between -SbClPh3 and -SbCl2Ph2 derivatives 6 and 7, respectively, consistent with a change from a bonding to a non-bonding interaction in response to relatively small modification in Lewis acidity of the acceptor. In the SbIII series, two geometric forms are observed. The P-Sb bond length in the SbCl2 derivative 2 is as expected for a normal (rather than a dative) bond. Rather unexpectedly, the phosphine-stiborane complexes 5-9 represent the first examples of the σ4P→σ6Sb structural motif. A complex situation: The strength of a dative phosphine-stiborane (P-Sb) interaction increases with stepwise replacement of phenyl groups on antimony atom with chloride groups. As the Lewis acidity is increased in regular steps (see figure), essentially linear response is observed initially, however then a sudden change in the P-Sb distance takes place during one particular step. This is consistent with a sudden switch from a non-bonding to a bonding interaction, that is, a discrete rather than continuum response.
- Chalmers, Brian A.,Bühl, Michael,Athukorala Arachchige, Kasun S.,Slawin, Alexandra M. Z.,Kilian, Petr
-
p. 7520 - 7531
(2015/05/13)
-
- Phenylation of Organic Derivatives of Mercury, Silicon, Tin, and Bismuth with Pentaphenylantimony and Pentaphenylphosphorus
-
Pentaphenylantimony and -phosphorus react with arylmercury chlorides in toluene at room temperature to give diaryl derivatives of mercury in yields of up to 95%. The reactions of pentaphenylantimony and -phosphorus with silicon and tin halides involve ary
- Sharutin,Sharutina,Senchurin,Egorova,Ivanenko,Petrov
-
p. 202 - 203
(2007/10/03)
-
- Catalytic C-phenylation of methyl acrylate with tetraphenylantimony(v) halides and carboxylates
-
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
-
p. 1376 - 1379
(2007/10/03)
-
- Phenylation of Antimony(V) Organic Compounds with Pentaphenylantimony. The Structure of Tetraphenylantimony Chloride
-
Tetraphenylantimony chloride and bromide were synthesized through the reaction of pentaphenylantimony with diphenylantimony trichloride or tribromide taken at a molar ratio of 2:1 in toluene. When the initial compounds were taken at a molar ratio of 1:1, triphenylantimony dichloride or dibromide was formed. The phenylation of triphenylantimony sulfate with pentaphenylantimony yielded tetraphenylantimony sulfate. According to the X-ray diffraction data, the antimony atom in the tetraphenylantimony chloride molecule has a distorted trigonal bipyramidal configuration with the chlorine atom in the axial position. The Sb-Cl distance is equal to 2.686(1) and Sb-C distances are equal to 2.113(4) and 2.165(4) A (av. 2.130 A).
- Sharutin,Sharutina,Pakusina,Platonova,Zadachina,Gerasimenko
-
-
- Synthesis, characterization and antitumor activity of some arylantimony triphenylgermanylpropionates and crystal structures of Ph3GeCH(Ph)CH2CO2SbPh4 and [Ph3GeCH2CH(CH3)CO2] 2Sb(4-ClC6H4)3
-
A series of novel arylantimony(V) triphenylgermanylpropionates with the formula (Ph3GeCHR1CHR2CO2) nSbAr(5-n) (R1 = H, Ph; R2 = H, CH3; n = 1, 2) were synthesized and characterized by elemental analysis, IR, 1H-NMR, 13C-NMR and mass spectroscopy. The crystal structures of Ph3GeCH(Ph)CH2CO2SbPh4 and [Ph3GeCH2CH(CH3)CO2] 2Sb(4-ClC6H4)3 were determined by X-ray diffraction. The in vitro antitumor activities of some selected compounds against five cancer cells are reported.
- Ma, Yongqiang,Li, Jinshan,Xuan, Zhenai,Liu, Runchang
-
p. 235 - 242
(2007/10/03)
-
- Arylation of organotin halides with pentaarylantimony and pentaphenylbismuth
-
Pentaarylantimony and pentaphenylbismuth arylate oranotin halides R3SnX and R2SnX2 (R = Alk, Ar; X = Cl, Br) in toluene at room temperature to aryltin derivatives R3SnAr and R2SnArX (initial reagent molar ratio 1:1) or R2SnAr2 (2:1) in 78-95% yield.
- Sharutin,Sharutina,Senchurin,Kovaleva,Shcherbakov,Gladyshev
-
-
- Cleavage of Pentaphenyl Arsenic and Antimony Derivatives with Halogens and Interhalogens
-
Facile and specific cleavage of metal-carbon bond(s) has been found to occur when pentaphenyl-arsenic or-antimony derivatives are treated with halogens (Br2, I2) and inter-halogens (ICl, IBr) under controlled conditions.
- Raizada, Meenu Singh,Nigam, H. L.
-
p. 722 - 724
(2007/10/02)
-
- REACTIONS OF TETRAPHENYLANTIMONY MERCAPTIDES
-
Reactions of tetraphenylantimony mercaptides, Ph4SbSC6H4Y, with electrophilic species in chlorocarbon solutions are reported.With chloromethyl methyl sulphide, allyl halides, sulphenyl halide, acyl halides, halogens, and triphenyltin chloride, ready and complete halide-mercaptide exchanges occur.No allylic rearrangement is found in the reaction with trans-PhCH=CHCH2Br.In a competition reaction for ClCH2SMe, Ph4SbSC6H5 was shown to be only slightly (ca. 1.2 times) more reactive than Ph4SbSC6H4OMe-p.The initial sulphur-containing product of reaction with p-toluenesulphonyl chloride, namely the thiosulphonate, p-MeC6H4SO2SC6H4Y, reacts further with Ph4SbSC6H4Y to produce the disulphide, (YC6H4S)2.Benzoyl peroxide and Ph4SbSC6H4 provide PhSbOCOPh and disulphide.
- Wardell, James L.,Grant, Douglas W.
-
p. 121 - 130
(2007/10/02)
-