18156-38-2Relevant articles and documents
Heteroorganic betaines 3. * Reactions of betaines containing the +P-C-Si-S- fragment
Borisova,Zemlyanskii,Shestakova,Khrustalev,Ustynyuk,Chernyshev
, p. 933 - 941 (2007/10/03)
The [Ph3P+-CMe2-SiMe2-SEt]Br- salt was prepared by the reaction of betaine Ph3P+-CMe2SiMeR-S- (1a: R = Me) with EtBr. Acetylation of betaine 1a or Et3P+-CHMeSiMe2-S- (2a) afforded 2,2,6-trimethyl-1,3-dioxa-2-silacyclohex-5-ene-4-thione Me2SiOC(=S)CH=C(Me)O or the [Et3P+-CHMeSiMe2Cl]Cl- salt depending on the reagent ratio. The reactions of betaines 1a,b (1b: R = Ph) or 2 with compounds (R3Sn)2X (X = O or NMe) can be used for the generation of silanones [RMeSi=O] and silaneimines [RMeSi=NMe] in solutions. The reactivity of betaines Ph3P+-CHR1SiMeR2-S- (R1 = H or Me and R2 = Me or Ph) is determined by the equilibrium between the zwitterionic and ylide Ph3P=CR1SiMeR2SH tautomers that exist in solutions.
On the Problem of the Intermediate Formation of Silanone R2Si=O by Reactions of Silenes with Dinitrogen Oxide
Wiberg, Nils,Preiner, Gerhard,Schurz, Klaus
, p. 1407 - 1412 (2007/10/02)
The silaethene Me2Si=C(SiMe3)2 (1a; unstable; from 1a * Ph2C=MSiMe3 = 4) forms with N2O an unstable cycloadduct, which decomposes under isomerization or cleavage.It was not possible to decide clearly, whether the last reaction, which leads to (Me3Si)2CN2 and polymers with (Me2SiO)n groups, proceeds with intermediate formation of silanone Me2Si=O or not (no trapping product with Et3SiH, but with Me3SiCl).The silanimines Me2Si=NSitBu3 (2a; unstable; from 2a * tBu3SiN3 = 7) and tBu2Si=NSitBu3 (2b; metastable) form with N2O unstable cycloadducts, which, under participation of the silanimines, react into products (10) being composed of a molecular silanone and a molecule silanimine.As has been shown by trapping experiments with Et3SiH, Me3SiCl, or Me3SiOMe, latter reaction involves unstable free silanones Me2Si=O (3a) or tBuSi=O (3b) as intermediates. 3b, generated in benzene from 2b/NO2 in the presence of equimolar amounts of tetrahydrofuran (THF), obviously forms an adduct 3b*THF, which is trapped by excess 2b.When 3b is produced in THF as solvent, the silanone starts THF polymerization, indicating a high Lewis acidity of silanones.
REACTIONS OF ORGANOMETALLIC PEROXIDES OF THE SILICON SUBGROUP WITH PHOSPHATES AND PHOSPHITES
Gorbatov, V. V.,Yablokova, N. V.,Aleksandrov, Yu. A.,Ivanov, V. I.
, p. 1576 - 1578 (2007/10/02)
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