Electron-rich olefins. 3. Formation of the first N,N'-persilylated 1,4-diaminoethene via a 1,2,3-triazoline(4) intermediate with 8 cyclically conjugated p electrons and 3 neighboring nitrogen electron pairs
Exhaustive reductive silylation of 2-(trimethylsilyl)-1,2,3-triazole (I) using Me3SiCl/K yields (E)-(Me3Si)2NCH:CHN(SiMe3)2 (II) and N(SiMe3)3. Initial reductive 1,4-addn. to I leads to 1,2,3-tris(trimethylsilyl)-1,2,3-triazoline (III) as an intermediate, which is rapidly reduced and silylated further to give II. Partial p overlap within the five-membered ring of III is evident from NMR shifts and electron-transfer reaction with TCNE. Photoelectron spectroscopy of II and the lability of its radical cation, as studied by ESR, show that this system cannot adopt a planar conformation, in contrast to the tetrazene(2) analog. on SciFinder(R)
%0 Journal Article
%1 Bessenbacher.1989b
%A Bessenbacher, Christian
%A Kaim, Wolfgang.
%D 1989
%J Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences
%K ESR;conformation cation cleavage conformation;ring conjugation intermediate mechanism;triazole mechanism;triazoline photoelectron prepn radical reductive silyl silylation silyltriazole silyltriazole;silylation spectra;ethenediamine tetrasilyl tetrasilylethenediamine trisilyl
%N 5
%P 511--518
%R 10.1515/znb-1989-0502
%T Electron-rich olefins. 3. Formation of the first N,N'-persilylated 1,4-diaminoethene via a 1,2,3-triazoline(4) intermediate with 8 cyclically conjugated p electrons and 3 neighboring nitrogen electron pairs
%V 44
%X Exhaustive reductive silylation of 2-(trimethylsilyl)-1,2,3-triazole (I) using Me3SiCl/K yields (E)-(Me3Si)2NCH:CHN(SiMe3)2 (II) and N(SiMe3)3. Initial reductive 1,4-addn. to I leads to 1,2,3-tris(trimethylsilyl)-1,2,3-triazoline (III) as an intermediate, which is rapidly reduced and silylated further to give II. Partial p overlap within the five-membered ring of III is evident from NMR shifts and electron-transfer reaction with TCNE. Photoelectron spectroscopy of II and the lability of its radical cation, as studied by ESR, show that this system cannot adopt a planar conformation, in contrast to the tetrazene(2) analog. on SciFinder(R)
@article{Bessenbacher.1989b,
abstract = {Exhaustive reductive silylation of 2-(trimethylsilyl)-1,2,3-triazole (I) using Me3SiCl/K yields (E)-(Me3Si)2NCH:CHN(SiMe3)2 (II) and N(SiMe3)3. Initial reductive 1,4-addn. to I leads to 1,2,3-tris(trimethylsilyl)-1,2,3-triazoline (III) as an intermediate, which is rapidly reduced and silylated further to give II. Partial \textgreek{p} overlap within the five-membered ring of III is evident from NMR shifts and electron-transfer reaction with TCNE. Photoelectron spectroscopy of II and the lability of its radical cation, as studied by ESR, show that this system cannot adopt a planar conformation, in contrast to the tetrazene(2) analog. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Bessenbacher, Christian and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/20a341a252e531881c17054ad94bdee91/huebleriac},
doi = {10.1515/znb-1989-0502},
interhash = {c65d3ac595830d6ecadf2484822935b4},
intrahash = {0a341a252e531881c17054ad94bdee91},
issn = {0932-0776},
journal = {Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences},
keywords = {ESR;conformation cation cleavage conformation;ring conjugation intermediate mechanism;triazole mechanism;triazoline photoelectron prepn radical reductive silyl silylation silyltriazole silyltriazole;silylation spectra;ethenediamine tetrasilyl tetrasilylethenediamine trisilyl},
number = 5,
pages = {511--518},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Electron-rich olefins. 3. Formation of the first N,N'-persilylated 1,4-diaminoethene via a 1,2,3-triazoline(4) intermediate with 8 cyclically conjugated \textgreek{p} electrons and 3 neighboring nitrogen electron pairs},
volume = 44,
year = 1989
}
