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Lewis Base Catalyzed Selective Chlorination of Monosilanes
Author(s) -
Sturm Alexander G.,
Schweizer Julia I.,
Meyer Lioba,
Santowski Tobias,
Auner Norbert,
Holthausen Max C.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201803921
Subject(s) - chemistry , bifunctional , lewis acids and bases , catalysis , ether , chloride , alcohol , base (topology) , hydrogen bond , polymer chemistry , organic chemistry , medicinal chemistry , combinatorial chemistry , molecule , mathematics , mathematical analysis
A preparatively facile, highly selective synthesis of bifunctional monosilanes R 2 SiHCl, RSiHCl 2 and RSiH 2 Cl is reported. By chlorination of R 2 SiH 2 and RSiH 3 with concentrated HCl/ether solutions, the stepwise introduction of Si−Cl bonds is readily controlled by temperature and reaction time for a broad range of substrates. In a combined experimental and computational study, we establish a new mode of Si−H bond activation assisted by Lewis bases such as ethers, amines, phosphines, and chloride ions. Elucidation of the underlying reaction mechanisms shows that alcohol assistance through hydrogen‐bond networks is equally efficient and selective. Remarkably, formation of alkoxysilanes or siloxanes is not observed under moderate reaction conditions.