54008-64-9Relevant articles and documents
Adducts of sila-, germa-, and stannaethenes Me2E=C(SiMe3)2 (E = Si, Ge, Sn) with anthracene: Syntheses, structures, thermolyses
Wiberg, Nils,Wagner, Susanne,Vasisht, Sham-Kumar,Polborn, Kurt
, p. 1412 - 1420 (2007/10/03)
The [4 + 2] cycloadducts of Me2E=C(SiMe3)2 (E = Si, Ge, Sn) and anthracene are prepared by reaction of an excess of anthracene in benzene with the [2 + 2] cycloadduct of Me2Si=C(SiMe3)2 and Ph2C=NSiMe
Storing of the Labile Silaethene Me2Si=C(SiMe3)2 with N-Trimethylsilyl-benzophenoneimine Ph2C=NSiMe3
Wiberg, Nils,Preiner, G.,Wagner, G.,Koepf, H.,Fischer, G.
, p. 1055 - 1061 (2007/10/02)
N-Trimethylsilyl-benzophenoneimine Ph2C=NSiMe3 is able to "store" the silaethene Me2Si=C(SiMe3)2 (1), produced from Me2SiF-CLi(SiMe3)2, under formation of a - and -cycloadduct (2, 3), respectively.Above 60 deg C (above 120 deg C) 2 or 3 by the way of 1 transform into 1:5 mixture of 2 and 3 (into a 1:1 mixture of the dimer of 1 and the insertion product of 1 into the SiN-bond of Ph2C=NSiMe3).In the presence of 2,3-dimethyl-1,3-butadiene (dmb), 2 or 3 form by way of the reaction of the intermediate 1 with dmb a -cycloadduct (75percent) and an ene reaction product (25percent).The rate constants of the first order decomposition of 2 or 3 in the presence of dmb (80 deg C, solvents like Et2O, C6H6) are in the order of 2 E-4 s-1 (τ1/2 ca. 1 h) and 3 E-5 s-1 (τ1/2 ca. 6 h), respectively. - Key words: Silaethene Me2Si=C(SiMe3)2, Ph2C=NSiMe3-adduct, Kinetic Studies
On the Way to Silaethene Me2Si=C(SiMe3)2: Trisilylated Methanes (Me3Si)2(Me2XSi)CY (X=e. g. Hal, RO, RS; Y e. g. Br, Li)
Wiberg, Nils,Preiner, Gerhard,Schieda, Oswald
, p. 2087 - 2103 (2007/10/02)
Bromotrisilylmethanes (Me3Si)2(Me2XSi)CBr (1 - 15) are formed as a result of the reaction of (Me3Si)2(Me2PhSi)CBr (16) with iodine monochloride, bromine and iodine (X = Cl, Br, I) respectively, and also through the reaction of (Me3Si)2(Me2BrSi)CBr (1) with AgX (X = F, p-TolSO2, p-TolSO3, MesSO3, Ph2PO2, Ph2PO3, Ph2PO4) or MX (M = H, Li, Na; X = HO, RO, RS, Bu, Ph).Butyl- as well as phenyllithium convert bromotrisilylmethanes 1 - 16 at low temperatures into lithium derivatives (Me3Si)2(Me2XSi)CLi (1a - 16a).These are in some cases (X = R, RO) thermostable, whereas, in other cases they decompose more or less readily under LiX elimination and lead (in many cases via silaethene Me2Si=C(SiMe3)2) to the disilacyclobutane derivative 2 (17).Acids HZ (e. g.HCl, HOMe, Me3CBr) protonate the lithium compounds into (Me3Si)2(Me2XSi)CH as well as (Me3Si)2(Me2ZSi)CH.Butyl bromide converts the more stable lithium compounds (Me3Si)2(Me2XSi)CLi (X = R, RO, F, Ph2POn) into butyl derivatives (Me3Si)2(Me2XSi)CBu.
