Hydrosilylation in Aryliminopyrrolide-Substituted Silanes

L. Witteman; Tim Evers; Zhan Shu; Martin Lutz; Bert Klein Gebbink; Marc-etienne Moret

doi:10.1002/chem.201505033

Hydrosilylation in Aryliminopyrrolide-Substituted Silanes

L. Witteman, Tim Evers, Zhan Shu, Martin Lutz, Bert Klein Gebbink, Marc-etienne Moret^*

^*Corresponding author for this work

Sub Organic Chemistry and Catalysis

Utrecht University

Research output: Contribution to journal › Article › Academic › peer-review

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 (DippIMP)SiHMeCl (DippIMP=2-[N-(2,6-diisopropylphenyl)iminomethyl]pyrrolide), is stable towards hydrosilylation, but slow hydrosilylation is observed for (DippIMP)SiHCl2. Reaction of two equivalents of DippIMPH with HSiCl3 results in the hydrosilylation product (DippAMP)(DippIMP)SiCl (DippAMP=2-[N-(2,6-diisopropylphenyl)aminomethylene]pyrrolide), but the trisubsitituted (DippIMP)3SiH is stable. Monitoring the hydrosilylation reaction of (DippIMP)SiHCl2 reveals a reactive pathway involving ligand redistribution reactions to form the disubstituted (DippAMP)(DippIMP)SiCl as an intermediate. The reaction is strongly accelerated in the presence of chloride anions.

Original language	English
Pages (from-to)	6087-6099
Journal	Chemistry - A European Journal
Volume	22
Issue number	17
Early online date	1 Mar 2016
DOIs	https://doi.org/10.1002/chem.201505033
Publication status	Published - 18 Apr 2016

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HydrosilylationFinal published version, 1.23 MBLicence: Taverne

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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 (DippIMP)SiHMeCl (DippIMP=2-[N-(2,6-diisopropylphenyl)iminomethyl]pyrrolide), is stable towards hydrosilylation, but slow hydrosilylation is observed for (DippIMP)SiHCl2. Reaction of two equivalents of DippIMPH with HSiCl3 results in the hydrosilylation product (DippAMP)(DippIMP)SiCl (DippAMP=2-[N-(2,6-diisopropylphenyl)aminomethylene]pyrrolide), but the trisubsitituted (DippIMP)3SiH is stable. Monitoring the hydrosilylation reaction of (DippIMP)SiHCl2 reveals a reactive pathway involving ligand redistribution reactions to form the disubstituted (DippAMP)(DippIMP)SiCl as an intermediate. The reaction is strongly accelerated in the presence of chloride anions.",

author = "L. Witteman and Tim Evers and Zhan Shu and Martin Lutz and {Klein Gebbink}, Bert and Marc-etienne Moret",

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T1 - Hydrosilylation in Aryliminopyrrolide-Substituted Silanes

AU - Witteman, L.

AU - Evers, Tim

AU - Shu, Zhan

AU - Lutz, Martin

AU - Klein Gebbink, Bert

AU - Moret, Marc-etienne

PY - 2016/4/18

Y1 - 2016/4/18

N2 - 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 (DippIMP)SiHMeCl (DippIMP=2-[N-(2,6-diisopropylphenyl)iminomethyl]pyrrolide), is stable towards hydrosilylation, but slow hydrosilylation is observed for (DippIMP)SiHCl2. Reaction of two equivalents of DippIMPH with HSiCl3 results in the hydrosilylation product (DippAMP)(DippIMP)SiCl (DippAMP=2-[N-(2,6-diisopropylphenyl)aminomethylene]pyrrolide), but the trisubsitituted (DippIMP)3SiH is stable. Monitoring the hydrosilylation reaction of (DippIMP)SiHCl2 reveals a reactive pathway involving ligand redistribution reactions to form the disubstituted (DippAMP)(DippIMP)SiCl as an intermediate. The reaction is strongly accelerated in the presence of chloride anions.

AB - 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 (DippIMP)SiHMeCl (DippIMP=2-[N-(2,6-diisopropylphenyl)iminomethyl]pyrrolide), is stable towards hydrosilylation, but slow hydrosilylation is observed for (DippIMP)SiHCl2. Reaction of two equivalents of DippIMPH with HSiCl3 results in the hydrosilylation product (DippAMP)(DippIMP)SiCl (DippAMP=2-[N-(2,6-diisopropylphenyl)aminomethylene]pyrrolide), but the trisubsitituted (DippIMP)3SiH is stable. Monitoring the hydrosilylation reaction of (DippIMP)SiHCl2 reveals a reactive pathway involving ligand redistribution reactions to form the disubstituted (DippAMP)(DippIMP)SiCl as an intermediate. The reaction is strongly accelerated in the presence of chloride anions.

U2 - 10.1002/chem.201505033

DO - 10.1002/chem.201505033

M3 - Article

SN - 0947-6539

VL - 22

SP - 6087

EP - 6099

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 17

ER -

Hydrosilylation in Aryliminopyrrolide-Substituted Silanes

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