80431-42-1Relevant articles and documents
Storing of the Labile Silaethene Me2Si=C(SiMe3)2 with Benzophenone
Wiberg, Nils,Preiner, Gerhard,Schurz, Klaus,Fischer, Gerd
, p. 1468 - 1474 (2007/10/02)
Benzophenone Ph2C=O is able to "store" the silaethene Me2Si=C(SiMe3)2 (1), produced from Me2SiX-CLi(SiMe3)2 (X = F, Br, Ph2PO4), under formation of a cycloadduct (2b).At about 100 deg C, 2b by way of 1 transfers into the cycloadduct of 1 and Ph2C=O (3b), which in the course of transformation decomposes visibly (in the absence of Me3SiCl) or only by traces (in the presence of Me3SiCl) to secondary products.In the presence of ROH (R = H, Me, tBu, MeCO) or PhN=NSiMe3 or RN3 (R = tBu, Me3Si) or 2,3-dimethylbutadiene (dmb) about 100 deg C 2b and 3b form by way of 1 insertion products of 1 into the OH bond of ROH or a cycloadduct of 1 and PhN=NSiMe3 or cycloadducts of 1 and RN3 or cycloadduct and an ene reaction product of 1 and dmb.The rate constants/half lives of the first order transformation of 2b into 3b or of the first order decomposition of 2b or of 3b in the presence of reactive traps for 1 (ROH, Me3SiN3; benzene as solvent) are in the order of 0.3E-4 s-1/τ1/2 = 7 h (2b --> 3b; 90 deg C) 3E-4 s-1/τ1/2 = 3/4 h (2b + traps; 90 deg C), 0.4E-4 s-1/τ1/2 = 5 h (3b + traps, 110 deg C). - Keywords: Silaethene Me2Si=C(SiMe3)2, Insertions, Cycloadditions, Kinetic Studies
Reaktivitaet des Silaethens Me2Si=C(SiMe3)2: Thermolyse von (Me3Si)2(Me2XSi)CLi (X z. B. (PhO)2PO2) in Anwesenheit von Silaethen-Faengern
Wiberg, Nils,Preiner, Gerhard,Schieda, Oswald
, p. 3518 - 3532 (2007/10/02)
Silaethene Me2Si=C(SiMe3)2 (1), generated as a reaction intermediate by the thermal elimination of LiX from Me2XSi-CLi(SiMe3)2, combines with the reactants a - b (e. g.Me3Si-Cl, Me3Si-OMe) with insertion in the a - b bond, with a = b - c - H (e. g.CH2=CMe