- Cleavage Reactions of some Phenyltin Compounds with Iodine Halides, -Pseudohalides and -Carboxylates
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Cleavage reactions of iodinehalides, -pseudohalides IX (X = Cl, Br, NCO, NCS, N3 and CN) with Ph3SnCp yield triphenyltinhalides, -pseudohalides (Ph3SnX) indicating cleavage of Cp-Sn bond in preference to Ph-Sn bond, and cleavage reactions of iodine carboxylates IX′ (X′ = CH3OCO, C5H5OCO, C6H5CH2OCO, o-NH2C6H4OCO, o-CIC6H4OCO, p-NO2C6H4OCO, p-NH2C6H4OCO, C6H5CH =CHOCO) (in situ) with Ph3SnCl give hitherto unknown diphenylchlorotin carboxylates (Ph2SnX′Cl) indicating cleavage of Ph-Sn bond in preference to Cl-Sn bond. On the basis of the results, it is predicated that these diphenylchlorotin carboxylates possess bridging carboxylate groups (inter-molecularly chelated structure) in the solid state, whereas in solution they contain chelated carboxylate groups (intra-molecularly chelated structures).
- Srivastava,Singh,Tangri,Sinha,Bajpai
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p. 443 - 445
(2007/10/03)
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- HALOGEN AND PEUDOHALOGEN SUBSTITUTION OF SOME ADAMANTANOID CHALCOGENATE CLUSTERS (2-) USING METHYLMERCURY AND TRIPHENYLTIN DERIVATIVES. A MULTINUCLEAR NUCLEAR MAGNETIC RESONANCE STUDY
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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.
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p. 2443 - 2451
(2007/10/02)
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- SYNTHESIS OF TRIPHENYLPHOSPHONOPROPIONBETAINETRIORGANOTIN(IV) SALTS +X-, BY NUCLEOPHILIC DISPLACEMENT OF ANIONS FROM TRIORGANOTINS
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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.
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p. 257 - 276
(2007/10/02)
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