108149-05-9Relevant academic research and scientific papers
Adduct Formation and Reactivity of Silane- and Germaneimines Me2E=NR (E = Si, Ge)
Wiberg, Nils,Preiner, Gerhard,Karampatses, Petros,Kim, Chung-Kyun,Schurz, Klaus
, p. 1357 - 1368 (2007/10/02)
Silane- and Germaneimines Me2E=NR (E = Si, Ge; R = silyl), generated as reactive intermediates by thermal cycloreversion from cycloadducts of Me2E=C(SiMe3)2 or Me2E=NR with silyl azides RN3, combine with reactants a (e.g.NEtMe2) under addition (formation of adducts 7), with a-b under insertion into the a-b bond (formation 13-16), with a=b (e.g.RN=EMe2, O=CPh2) under cycloaddition (e.g. formation of 17, 18), with a=b=c (e.g.R'N=N=N) under cycloaddition (e.g. formation of 19, 20), and with a=b-c-H (e.g.CH2=CR-CH2-H, O=CMe-CH2-H) under ene reaction (formation of 21-24). cycloaddition of Me2Si=NR with organic 1,3-dienes (e.g.CH2=CR-CR=CH2, cyclopentadiene) is not observed.By comparison with ethenes Me2E=C(SiMe3)2, imines Me2E=NR have greater tendency for insertion and lesser tendency for cycloaddition; by comparison with silaneimines Me2Si=NR, germaneimines Me2Ge=NR are possibly less Lewis acidic.
Preparation of Silan- and Germanimines Me2E=NR (E = Si, Ge) from Sila- and Germadihydrotriazoles
Wiberg, Nils,Karampatses, Petros,Kim, Chung-Kyun
, p. 1203 - 1212 (2007/10/02)
Sila- or germaethene Me2E=C(SiMe3)2 quantitatively react with azidoalkanes or -silanes RN3 nMe3-nSi, Ph3Si, (Me3Si)2NMe2E, Me2SiN3> at -78 deg C by cycloaddition to form sila- or germadihydrotriazoles 3 and 4, respectively.The latter decompose partly below (E = Si, R = silyl), partly at or above room temperature (E = Si, R = alkyl; E = Ge) in a first-order reaction by isomerization into diazomethane derivatives as well as by cycloreversion into (Me3Si)2C=N=N and silan- or germanimines Me2E=NR (rate constants: Table 1).The saturated compounds Me2E= NR are formed as short-lived intermediates.Their stabilization, as a rule, takes place by dimerization and, in exceptional cases, by reaction with the silan- or germanimine sources (R = SiMe3) or by intramolecular migration processes .
