- Triphenyltin Iodide
-
The geometry at the Sn atom in iodotriphenyltin, , is distorted tetrahedral.
- Ng, Seik Weng
-
-
Read Online
- SYNTHESIS OF TRIPHENYLPHOSPHONOPROPIONBETAINETRIORGANOTIN(IV) SALTS +X-, BY NUCLEOPHILIC DISPLACEMENT OF ANIONS FROM TRIORGANOTINS
-
Trimethyl- and triphenyl-tin(IV) hydroxide act on triphenyl(2-carboxyethyl)-phosphonium hydrochloride, which is made from 3-chloropropionic acid and triphenylphosphine, to release water in the presence of dimethylformamide (DMF) as a catalyst.The water is azeotropically distilled to drive the reaction forward and produce triphenylphosphonopropionbetainetrimethyl- and triphenyl-tin(IV) chlorides in high yield.The latter product also results from the displacement of chloride from triphenyltin(IV) chloride by the phosphobetaine, (C6H5)3P(CH2)2CO2, which is made by treating the phospnonium hydrochloride with bicarbonate, and the compounds + X- where X = Cl, Br, I, N3, NCS, NO3, B(C6H5)4 and Co(CO)4 are made in the same way.The acetate salt results from metathesis from the chloride and lead(II) acetate.A double salt, + -, is formed for X = Cl, Br, and N3 by adding additional (C6H5)3SnX to the already-formed simple salts.Double salts are also obtained from the 1/1 reactions between the phosphobetaine and triphenyltin(IV) isocyanate and methyldiphenyltin(IV) chloride.The phosphonium chloride double salt could be converted to the thiophosphonium derivative by heating with elemental sulfur in ethanol.The products of these novel nucleophilic displacement reactions are high melting solids.Tin-119m Moessbauer data are consistent with five-coordinated, triorganotin(IV) formulations with the exception of the diphenyl(8-hydroxyquinolinato)tin(IV) chloride salt in which the tin atom is six-coordinated, and the diphenyltin system cis-oriented.The parameters otherwise do not change with the nature of the X group, which in the tetracarbonylcobaltate derivative is tetrahedral by infrared, establishing the ionicity of the products.The chloride exhibits a molar conductivity indicative of a 1/1 electrolyte in DMF.A bridging acetate structure in the solid is consistent with the lowered v(CO2) frequencies.The Moessbauer spectra of the double salts give simple doublets of lowered isomer shift (IS) and raised quadrupole splitting (QS) which may arise from a cross-linking ion pairing of the...
- Ng, S. -W.,Zuckerman, J. J.
-
-
Read Online
- PREPARATION AND SPECTROSCOPIC STUDIES OF SOME CYCLIC UREA ADDUCTS OF TRIPHENYL-THIN AND -LEAD HALIDES
-
1,3-Dimethyl-2-imidazolidinone (dimethylethylene urea, DMEU) and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (dimethylpropylene urea, DMPU) adducts of the type Ph3SnX*L (X = Cl, Br and I), Ph3PbX*L (X = Br, I), 3Ph3PbCl*2DMEU and 2Ph3PbCl*DMPU have been prepared and characterized.Assignments are made for ν(CO) and ν(CN) frequencies in the IR, and for skeletal frequencies observed in both IR and Raman spectra in the range 400 to 100 cm-1.Infrared measurements show that the adducts are bound through the carbonyl oxygen, and are highly dissociated in dichloromethane solution. 1H and 119 Sn or 207Pb NMR measurements reveal that ligand exchange, fast on the NMR time scale, occurs in solution.Coordination of the ligand causes a large upfield shift in the 119Sn or 207Pb resonances, but Ph3MI*L have shifts similar to those for the parent iodides, indicating almost complete dissociation.Thermodynamic parameters are reported for the dissociation of Ph3SnX*DMPU (X = Cl, Br) in Ch2Cl2 solution
- Aitken, Clare T.,Onyszchuk, Mario
-
-
Read Online
- Synthesis and reactions of the tungsten nonheteroatom-stabilised carbene anion -
-
Treatment of CpW(SnPh3)(CO)2(=CHPh) with I2 gives the nonheteroatom-stabilised carbene complex (CpWI(CO)2(=CHPh), whose reduction by NaC10H8 gives the nonheteroatom stabilised carbene anion -, the first member of a new class of
- Winter, Mark J.,Woodward, Simon
-
-
Read Online
- Reactions of organolanthanide compounds RLnI (Ln = Yb, Eu, Sm) with organic derivatives of silicon, tin, lead, and antimony
-
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
-
p. 244 - 246
(2007/10/03)
-
- Easy general method for interhalide conversions in organotin compounds
-
The halides in organotin halides are easily interconverted in excellent yields using aqueous ammonium halide solutions and various organic solvents.
- Zobel, Bernhard,Lim, Allan E. K.,Dunn, Kerri,Dakternieks, Dainis
-
p. 4889 - 4890
(2008/10/08)
-
- Cleavage of Sn-Sn Bonds in Hexaalkyl(aryl)stannanes under the Action of Yb(II) Derivatives
-
Ytterbium(II) derivatives MeYbI, PhYbI, and YbI2 cleave the Sn-Sn bond in distannanes R′3-SnR′3 (R′ = n-Bu, Ph) to give heterobimetallic derivatives R′3SnYbI, which were identified by products of their hydrolysis, exchange with R″3EHlg (R″ = Ph, Me; E = Ge, Si, Sn) and cross coupling with MeI in the presence of NiCl2(Ph3P)2.
- Syutkina,Rybakova,Novgorodova,Petrov
-
-
- Organotin Biocides. XIII. C-Triorganostannylimidazoles, -benzoxazoles and -benzothiazoles
-
The synthesis, spectroscopic characterisation, and reactivity of a series of triorganotin imidazoles, benzothiazoles and benzoxazoles R3Sn(Het) (R=Me, Bu, Ph) are described.The structure of 2-(triphenylstannyl)benzothiazole has been determined by crystallographic methods.Space group: Triclinic, P1; a 9.501(1), b 10.172(2), c 13.231(2) Angstroem, β 70.46(1), γ 69.71(1) deg, U 1082.8 Angstroem3, F(000)=484, μ(Mo-Kα) 11.74 cm-1, R=0.0719 for 2264 reflections with I>3?I.The geometry at the tin is tetrahedral.Bond angles at tin are used to discuss the reactivity and Moessbauer spectra of these species.
- Molloy, Kieran C.,Waterfield, Philip C.,Mahon, Mary F.
-
-
- HALOGEN AND PEUDOHALOGEN SUBSTITUTION OF SOME ADAMANTANOID CHALCOGENATE CLUSTERS (2-) USING METHYLMERCURY AND TRIPHENYLTIN DERIVATIVES. A MULTINUCLEAR NUCLEAR MAGNETIC RESONANCE STUDY
-
Multinuclear nmr (1H, 77Se, 111/113Cd, 119Sn, 199Hg, as appropriate) has been used to study Y(1-) - EPh(1-) exchange in Me2CO or MeCN between (RnM'Y (RnM' = Ph3Sn or MeHg; Y = Cl, Br, I, NCO, or NCS) and the adamantane-like anions (2-) (E = S, M = Zn, Cd, or Co; E = Se, M = Zn or Cd), as their tetraalkylammonium salts.Quantitative terminal substitution of the clusters occurs in most cases, giving 4-x(MY)x>(2-) (x = 1-4).However, reaction is incomplete for M = Cd, E = S or Se, RnM'Y = Ph3SnNCO or Ph3SnNCS and for M = Zn or Co, E = S, RnM'Y = MeHgI.Differences in the extents of reaction for Ph3SnY and MeHgY are consistent with the position of equilibrium in MeHgY:Ph3SnEPh mixtures.Group interchange provides a convenient alternative synthesis of the known halogen-substituted clusters (2-) (M = Zn or Cd, Y = Cl, Br, or I; M = Co, Y = Cl), and the first syntheses of (2-) (Y = Br or I) and various pseudohalogen-substituted adamantanoid anions.The nuclei used for full direct nmr characterization of the new clusters in solution were: 77Se and 113Cd for 4-x(CdY)x>(2-) (x = 1-4; Y = NCO or NCS); 77Se for 4-x(ZnY)x>(2-) (x = 1-4, Y = NCO or NCS); 113Cd for 4-x(CdY)x>(2-) (x = 1-4; Y = NCO or NCS); 1H for (2-) (Y = Br, I, NCO, or NCS).The first solution 1H nmr spectrum of (2-) is also reported.
- Dean, Philip A. W.,Vittal, Jagadese J.
-
p. 2443 - 2451
(2007/10/02)
-
- Weak carbon-carbon bonds. Synthesis, structure, and reactions of 7-Methyl-1,3,5-triphenyl-2,4,9-trithia-1,3,5-tristannaadamantane
-
7-Methyl-1,3,5-triphenyl-2,4,9-trithia-1,3,5-tristannaadamantane (1-CH3) was synthesized to test the possibility that a carbon-methyl bond activated by three antiperiplanar carbon-tin bonds might be a reactive donor of methyl. MNDO calculations suggest that the strength of the carbon-methyl bond in compound 1-CH3 should be about 40 kcal/mol. Nevertheless, the reactivity of this bond is not conspicuously high. This is presumably because the methyl group is neopentylic and sterically hindered and because other weak bonds in compound 1-CH3 are even more reactive and obscure the intrinsic activation of the carbon-methyl bond by making reactions occur elsewhere.
- Gallant, Michel,Kobayashi, Michio,Latour, Stéphan,Wuest, James D.
-
p. 736 - 739
(2008/10/08)
-
- Synthesis and Reactions of Some Phenylcyclopentadienyltin Compounds
-
Cyclopentadienylthallium (CpTl) reacts with Ph2SnCl2 and Ph3SnI to yield Ph2SnCpCl and Ph3SnCp respectively.Ph3SnCp reacts with I2 to afford Ph3SnI, indicating preferential cleavage of Cp-Sn bond by I2 over the Ph-Sn bond.
- Srivastava, P. C.,Srivastava, S. K.
-
p. 776 - 777
(2007/10/02)
-
- Reactions of Tin-Naphthyl Bond with Halogens and Pseudohalogens
-
Reactivity of Sn-phenyl or Sn-naphthyl bond in tetraorganotins, PhnSnNp4-n (Ph = phenyl, Np = α-naphthyl; n = 2,3) towards halogens (Br2 and I2), interhalogens (IBr and ICl), interpseudohalogens (BrCN and ICN) and pseudohalogen (SCN)2 has been studied.It is found that the Sn-Np bond is preferentially cleaved yielding in most cases phenyltin derivatives along with the corresponding α-naphthyl halides.
- Bhattacharya, S. N.,Husain, Ishrat
-
p. 1119 - 1121
(2007/10/02)
-
- METAL-HALOGEN BONDING STUDIES WITH GROUP IV A TRIALKYLMETAL HALIDES
-
Halogen redistribution reactions have been found to take place between benzyl bromide or benzyl iodide and the Group IV A silicon, germanium, tin, and lead containing trialkylmetal chlorides.However, for the reactions of the Si, Ge and Sn compounds, a quaternary ammonium halide catalyst was necessary to enable the equilibria to be established at reasonably rapid rates.The equilibrium constants at 50 deg C have been measured for each of these halogen redistributions.They have been found to increase gradually on going down in Group IV A from silicon to lead, being conside rably less than unity in the case of silicon and somewhat greater than unity in the case of lead for both the R3MCl + BzBr and R3MCl + BzI reactions.The ΔG0 values for these equilibria have been calculated, and it is suggested that their differences may be explained in terms of the relative importance of p?-d? contributions to the halogen-metal bonding in the various Group IV A trialkylmetal halide systems.
- Friedrich, Edwin C.,Abma, Charles B.,Vartanian, Paul F.
-
p. 203 - 212
(2007/10/02)
-