- Organosilicon and organotin derivatives of urea in transmetallation reactions
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Reaction of N-trimethylsilyl-N′-phenylurea with bis(tributylstannyl) oxide in refluxing THF yields tributylstannyl isocyanate and aniline as the main products, while in the case of triphenylstannyl chloride N-triphenylstannyl-N′-phenylurea can be prepared. Its thermal decomposition yields triphenylstannyl isocyanate and aniline. Reaction of N,N′-bis(trimethylstannyl)urea with (Bu3Sn)2O gives Bu3Sn-N=C=O, HMDS, and ammonia.
- Gordetsov,Kulagina,Zimina
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p. 409 - 412
(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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