%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 = {2022-06-15T11:26:56.000+0200}, author = {Baumgarten, Jens and Bessenbacher, Christian and Kaim, Wolfgang and Stahl, Thomas.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2f7bcf10d1ee591ef8f27da61f0c8a4f6/huebleriac}, 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 = {2022-06-15T09:26:56.000+0200}, title = {Molecular and electronic structure of electron-transfer active main-group organometallics}, volume = 111, year = 1989 }