117984-23-3Relevant academic research and scientific papers
Reaction of the (dichloromethyl)oligosilanes R(Me3Si)2Si - CHCl2 (R = Me, Ph, Me3Si) with organolithium reagents and the synthesis of novel kinetically stabilized silenes
Schmohl, Kathleen,Reinke, Helmut,Oehme, Hartmut
, p. 481 - 489 (2007/10/03)
The dichloromethyloligosilanes R1(Me3Si)2Si - CHCl2 (1a,b) (1a: R1 = Me; 1b: R1 = Ph), prepared by treatment of methylbis(trimethylsilyl)silane or phenylbis(trimethylsilyl)silane respective
Thermal Stabilization of the Silaethene Ph2Si=C(SiMe3)2
Wiberg, Nils,Link, Matthias
, p. 1241 - 1250 (2007/10/03)
Silaethene Ph2Si=C(SiMe3)2 (3) (generated from Ph2SiBr-CLi(SiMe3)2 = 3*LiBr in Et2O at -78 deg C) reversibly isomerizes fast by methyl migration, then a bit slower by phenyl migration, and finally fast by methyl migration into thermodynamically more stable Me2Si=C(SiMePh2)(SiMe3) (3a), then into medium stable PhMeSi=C(SiMe2Ph)(SiMe3) (3b), and finally into most stable Me2Si=C(SiMe2Ph)2 (3c) (cf.Schemes 1 and 2; Figure 1).Simultaneously with isomerization 3a -> 3c cycloadditions (dimerizations) of 3a and 3c occur (formation of 3a * 3a, 3a * 3c, 3c * 3c; cf.Scheme 2).Over and above that, silaethenes 3a and 3c irreversibly isomerize into disilaindanes 4a, 4b, and 4c (cf.Scheme 6).Certainly, the latter reactions are even slow at 100 deg C.Thermolysis of 3a * 3a, 3a * 3c, 3c * 3c at 340 deg C, on the other hand, leads by way of cycloreversion and the intermediate formation of an equilibrium mixture of 3, 3a, 3b, 3c almost quantitatively to 4.In addition to the thermolysis products mentioned above, products of 3 and its isomers 3a, 3b, 3c with the solvents (for example Et2O; cf.Scheme 7), with the silaethene sources (for example 3 * LiBr; cf.Scheme 8), or with products formed from sources besides silaethene 3 (for example Ph2C=N-SiMe3; cf.Scheme 4) are observed. - Keywords: Methyl and phenyl group migrations in Ph2Si=C(SiMe3)2 ; Silaethenes Me2Si=C(SiMePh2)(SiMe3), PhMeSi=(SiMe2Ph)(SiMe3), Me2Si=C(SiMe2Ph)2 ; Silaethene dimers ; Disilaindanes ; Silaethene reactions with Et2O and with Ph2SiBr-CLi(SiMe3)2 ; Insertions of silaethenes into SiN bond of Ph2C=N-SiMe3
Anchimeric assistance in the reactions of the crowded organosilicon iodide (Me3Si)2(Ph2MeSi)CSiMe2I with electrophiles
Al-Gurashi, Mohammad A. M. R.,Ayoko, G. Adefikayo,Eaborn, Colin,Lickiss, Paul D.
, p. 517 - 521 (2007/10/02)
The relative reactivities of the iodides (Me3Si)2(Ph2MeSi)CSiMe2I, 1, (Me3Si)2(PhMe2Si)CSiMe2I, 2, (Me3Si)3CSiPhMeI 3, (Me3Si)3CSiPh2I, 4, and (Me3Si)3CSiMe2I, 5, towards silver salts or ICl have been studied and the results support the proposal that for
Generation and Detection of the Silaethene Ph2Si=C(SiMe3)2
Wiberg, Nils,Link, Matthias,Fischer, Gerd
, p. 409 - 418 (2007/10/02)
Bromotrisilylmethanes (Me3Si)2(Ph2XSi)CBr (4-13; Table 1) are formed by the reaction of (Me3Si)2(Ph2HSi)CM (M = Li, Na) with bromine or with bromine/chlorine (X = H, Cl, Br) and also by treating (Me3Si)2(Ph2BrSi)CBr with KHF2 (X = F), H2O or MeOH (X = OH, OMe), MeLi (X = Me), BuLi/Br2 (X = Bu), PhLi/Br2 or PhLi/PhOLi/Br2 (X = Ph, OPh).PhLi, BuLi, and tBu3SiNa convert the bromotrisilylmethanes by Br/M exchange into compounds (Me3Si)2(Ph2XSi)CM, which may be protolyzed, alkylated, and brominated .For X = halogen the equilibrium (Me3Si)2(Ph2XSi)CM Ph2Si=C(SiMe3)2 (3) + MX exists.Thereby, silaethene 3 is formed in Et2O at -78 deg C (X/M = Br/Li) or at room temperature (X/M = F/Li, Br/Na), respectively, reversibly in low concentrations and at higher temperatures irreversibly (formation of secondary products of 3).The intermediacy of 3 has been established chemically by trapping 3 with (for example) RLi (formation of insertion products in the R-Li bond), Ph2C=NSiMe3 (formation of a cycloadduct, which may serve as a source of 3), tBu2MeSiN3 (formation of a cycloadduct), and particularly 2,3-dimethyl-1,3-butadiene (formation of Diels-Alder and ene reaction products).In the last case products and yields are independent of the origin of 3.From Me2Si=C(SiMe3)2 (1) to 3 there is only a gradual (but no principal) change of silaethene reactivity (3 is more Lewis acidic than 1). - Keywords: Silaethenes/ Bromotris(silyl)methane derivatives
