title: Hydrosilylation in Aryliminopyrrolide-Substituted Silanes.
abstract: A range of silanes was synthesized by the reaction of HSiCl3 with iminopyrrole derivatives in the presence of NEt3 . 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)SiHCl2 . Reaction of two equivalents of (Dipp) IMPH with HSiCl3 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)SiHCl2 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.
authors.affiliation: Department of Chemistry, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
authors.forename: Léon
authors.identifier: http://orcid.org/0000-0003-2189-830X
authors.initials: L
authors.lastname: Witteman
authors.affiliation: Department of Chemistry, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
authors.forename: Tim
authors.initials: T
authors.lastname: Evers
authors.affiliation: Department of Chemistry, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
authors.forename: Zhan
authors.initials: Z
authors.lastname: Shu
authors.affiliation: Crystal and Structural Chemistry, Bijvoet Center for Biomolecular Research, Faculty of Science, Utrecht University, Padualaan 8, 3584 CH, Utrecht, The Netherlands.
authors.forename: Martin
authors.initials: M
authors.lastname: Lutz
authors.affiliation: Department of Chemistry, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
authors.forename: Robertus J M
authors.identifier: http://orcid.org/0000-0002-0175-8302
authors.initials: RJ
authors.lastname: Klein Gebbink
authors.affiliation: Department of Chemistry, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands. m.moret@uu.nl.
authors.forename: Marc-Etienne
authors.identifier: http://orcid.org/0000-0002-3137-6073
authors.initials: ME
authors.lastname: Moret
keywords: density functional calculations; hydrosilylation; hypervalent compounds; ligand effects; silicon