TY - JOUR
T1 - Tuning the Lewis Acidity of Neutral Silanes Using Perfluorinated Aryl- and Alkoxy Substituents
AU - Tschernuth, Florian S.
AU - Bichlmaier, Lukas
AU - Stigler, Sebastian
AU - Inoue, Shigeyoshi
N1 - Publisher Copyright:
© 2023 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.
PY - 2023/11/2
Y1 - 2023/11/2
N2 - The emerging field of Lewis acidic silanes demonstrates the versability of molecular silicon compounds for catalytic applications. Nevertheless, when compared to the multifunctional boron Lewis acid B(C6F5)3, silicon derivatives still lack in terms of reactivity. In this regard, we demonstrate the installation of perfluorotolyl groups (TolF) on neutral silicon atoms to obtain the respective tetra- and trisubstituted silanes Si(TolF)4 and HSi(TolF)3. These compounds were fully characterized including SC-XRD analysis but unexpectedly showed no significant Lewis acidity. By using strongly electron-withdrawing perfluorocresolato groups (OTolF) the tetrasubstituted silane Si(OTolF)4 was obtained, bearing an 8 % increased Δδ(31P) shift when applying the Gutmann-Beckett method, compared to literature-known Si(OPhF)4. Ultimately the heteroleptic Si(PhF)2pinF was successfully synthesized and fully characterized including SC-XRD analysis, introducing a highly Lewis acidic silicon atom holding two silicon-carbon bonds.
AB - The emerging field of Lewis acidic silanes demonstrates the versability of molecular silicon compounds for catalytic applications. Nevertheless, when compared to the multifunctional boron Lewis acid B(C6F5)3, silicon derivatives still lack in terms of reactivity. In this regard, we demonstrate the installation of perfluorotolyl groups (TolF) on neutral silicon atoms to obtain the respective tetra- and trisubstituted silanes Si(TolF)4 and HSi(TolF)3. These compounds were fully characterized including SC-XRD analysis but unexpectedly showed no significant Lewis acidity. By using strongly electron-withdrawing perfluorocresolato groups (OTolF) the tetrasubstituted silane Si(OTolF)4 was obtained, bearing an 8 % increased Δδ(31P) shift when applying the Gutmann-Beckett method, compared to literature-known Si(OPhF)4. Ultimately the heteroleptic Si(PhF)2pinF was successfully synthesized and fully characterized including SC-XRD analysis, introducing a highly Lewis acidic silicon atom holding two silicon-carbon bonds.
KW - Childs method
KW - Gutmann-Beckett method
KW - Lewis acids
KW - perfluorotolyl ligands
KW - silanes
UR - http://www.scopus.com/inward/record.url?scp=85170202247&partnerID=8YFLogxK
U2 - 10.1002/ejic.202300388
DO - 10.1002/ejic.202300388
M3 - Article
AN - SCOPUS:85170202247
SN - 1434-1948
VL - 26
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 31
M1 - e202300388
ER -