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Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes
Author(s) -
Witteman Léon,
Evers Tim,
Shu Zhan,
Lutz Martin,
Klein Gebbink Robertus J. M.,
Moret MarcEtienne
Publication year - 2016
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.201505033
Subject(s) - hydrosilylation , chemistry , steric effects , medicinal chemistry , silanes , substituent , ligand (biochemistry) , intramolecular force , stereochemistry , organic chemistry , catalysis , silane , biochemistry , receptor
A range of silanes was synthesized by the reaction of HSiCl 3 with iminopyrrole derivatives in the presence of NEt 3 . In certain cases, intramolecular hydrosilylation converts the imine ligand into an amino substituent. This reaction is inhibited by factors such as electron‐donating substitution on Si and steric bulk. The monosubstituted ( Dipp IMP)SiHMeCl ( Dipp IMP=2‐[ N ‐(2,6‐diisopropylphenyl)iminomethyl]pyrrolide), is stable towards hydrosilylation, but slow hydrosilylation is observed for ( Dipp IMP)SiHCl 2 . Reaction of two equivalents of Dipp IMPH with HSiCl 3 results in the hydrosilylation product ( Dipp AMP)( Dipp IMP)SiCl ( Dipp AMP=2‐[ N ‐(2,6‐diisopropylphenyl)aminomethylene]pyrrolide), but the trisubsitituted ( Dipp IMP) 3 SiH is stable. Monitoring the hydrosilylation reaction of ( Dipp IMP)SiHCl 2 reveals a reactive pathway involving ligand redistribution reactions to form the disubstituted ( Dipp AMP)( Dipp IMP)SiCl as an intermediate. The reaction is strongly accelerated in the presence of chloride anions.