期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 24, 页码 13656-13660出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202103414
关键词
benzoylium cations; C− X bond activation; main group complexes; silanes; weakly coordinating anions
资金
- Deutsche Forschungsgemeinschaft (Cluster of Excellence UniSysCat of Germany's Excellence Strategy) [EXC 2008-390540038]
- Einstein Stiftung Berlin
- Projekt DEAL
Si(OTf)(4) is a neutral silicon-based Lewis superacid suitable for reactions with both soft and hard Lewis bases. Its OTf groups have a dual function, forming complexes with soft Lewis donors and cleaving C-X bonds of hard organic Lewis bases to form SiX4 products.
A facile synthesis and isolation of pristine silicon tetrakis(trifluoromethanesulfonate), Si(OTf)(4), is reported, acting as the first neutral silicon-based Lewis superacid suitable towards soft and hard Lewis bases. Its OTf groups have a dual function: they are excellent leaving groups and modulate the degree of reactivity towards soft and hard Lewis bases. Exposed to soft Lewis donors, Si(OTf)(4) leads to [L2Si(OTf)(4)] complexes (L=isocyanide, thioether and carbonyl compounds) with retention of all Si-OTf bonds. In contrast, it can cleave C-X bonds (X=F, Cl) of hard organic Lewis bases with a high tendency to form SiX4 (X=F, Cl) after halide/triflate exchange. Most notable, Si(OTf)(4) allows a gentle oxydefluorination of mono- and bis(trifluoromethyl)benzenes, resulting in the formation of the corresponding benzoylium species, which are stabilized by the weakly coordinating [Si(OTf)(6)] dianion.
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