The mol. structure of the single-electron-transfer (SET) reagent 1,4-bis(triisopropylsilyl)-1,4-dihydropyrazine (I) has a virtually planar ring system with 8 conjugating p electrons, effectively shielded N-Si bonds, and nonbonded contacts between ring and iso-Pr H atoms. I undergoes an electrochem. reversible one-electron oxidn. at a very low potential; electronic and steric stabilization as well as an apparently small geometry change on oxidn. make this mol. highly suitable for the study of outer-sphere SET processes. The color of yellow I and of related compds. is attributed to weak p $\rightarrow$ s*(Si-C) transitions whereas the reverse assignment s(M-C) $\rightarrow$ p* and opposite direction of inter- and intramol. electron transfer is noted for the intensely red isosteric bis(triisopropylaluminum) complex of pyrazine. The structural and electronic requirements and various manifestations of electron transfer from main-group organometallics are discussed. on SciFinder(R)
%0 Journal Article
%1 Baumgarten.1989
%A Baumgarten, Jens
%A Bessenbacher, Christian
%A Kaim, Wolfgang
%A Stahl, Thomas.
%D 1989
%J Journal of the American Chemical Society
%K crystal dihydro;SET potential reagent structure triisopropylsilyl triisopropylsilyldihydropyrazine;electrochem triisopropylsilyldihydropyrazine;mol triisopropylsilyldihydropyrazine;oxidn triisopropylsilyldihydropyrazine;pyrazine triisopropylsilyldihydropyrazine;silyldihydropyrazine
%N 6
%P 2126--2131
%R 10.1021/ja00188a028
%T Molecular and electronic structure of electron-transfer active main-group organometallics
%V 111
%X The mol. structure of the single-electron-transfer (SET) reagent 1,4-bis(triisopropylsilyl)-1,4-dihydropyrazine (I) has a virtually planar ring system with 8 conjugating p electrons, effectively shielded N-Si bonds, and nonbonded contacts between ring and iso-Pr H atoms. I undergoes an electrochem. reversible one-electron oxidn. at a very low potential; electronic and steric stabilization as well as an apparently small geometry change on oxidn. make this mol. highly suitable for the study of outer-sphere SET processes. The color of yellow I and of related compds. is attributed to weak p $\rightarrow$ s*(Si-C) transitions whereas the reverse assignment s(M-C) $\rightarrow$ p* and opposite direction of inter- and intramol. electron transfer is noted for the intensely red isosteric bis(triisopropylaluminum) complex of pyrazine. The structural and electronic requirements and various manifestations of electron transfer from main-group organometallics are discussed. on SciFinder(R)
@article{Baumgarten.1989,
abstract = {The mol. structure of the single-electron-transfer (SET) reagent 1,4-bis(triisopropylsilyl)-1,4-dihydropyrazine (I) has a virtually planar ring system with 8 conjugating \textgreek{p} electrons, effectively shielded N-Si bonds, and nonbonded contacts between ring and iso-Pr H atoms. I undergoes an electrochem. reversible one-electron oxidn. at a very low potential; electronic and steric stabilization as well as an apparently small geometry change on oxidn. make this mol. highly suitable for the study of outer-sphere SET processes. The color of yellow I and of related compds. is attributed to weak \textgreek{p} $\rightarrow$ \textgreek{s}*(Si-C) transitions whereas the reverse assignment \textgreek{s}(M-C) $\rightarrow$ \textgreek{p}* and opposite direction of inter- and intramol. electron transfer is noted for the intensely red isosteric bis(triisopropylaluminum) complex of pyrazine. The structural and electronic requirements and various manifestations of electron transfer from main-group organometallics are discussed. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Baumgarten, Jens and Bessenbacher, Christian and Kaim, Wolfgang and Stahl, Thomas.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2f7bcf10d1ee591ef8f27da61f0c8a4f6/b_schwederski},
doi = {10.1021/ja00188a028},
interhash = {632871a9c0fef4d5a0c694f46642a374},
intrahash = {f7bcf10d1ee591ef8f27da61f0c8a4f6},
issn = {0002-7863},
journal = {Journal of the American Chemical Society},
keywords = {crystal dihydro;SET potential reagent structure triisopropylsilyl triisopropylsilyldihydropyrazine;electrochem triisopropylsilyldihydropyrazine;mol triisopropylsilyldihydropyrazine;oxidn triisopropylsilyldihydropyrazine;pyrazine triisopropylsilyldihydropyrazine;silyldihydropyrazine},
number = 6,
pages = {2126--2131},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Molecular and electronic structure of electron-transfer active main-group organometallics},
volume = 111,
year = 1989
}