Please use this identifier to cite or link to this item: http://dx.doi.org/10.14279/depositonce-6270
Main Title: Peripheral mechanism of a carbonyl hydrosilylation catalysed by an SiNSi iron pincer complex
Author(s): Metsänen, Toni Tapio
Gallego, Daniel
Szilvasi, Tibor
Drieß, Matthias
Oestreich, Martin
Type: Article
Language Code: en
Abstract: Combined experimental and theoretical analysis of the carbonyl hydrosilylation catalysed by an iron(0) pincer complex reveals an unprecedented mechanism of action. The iron(0) complex is in fact a precatalyst that is converted into an iron(II) catalyst through oxidative addition of a hydrosilane. Neither the hydrogen atom nor the silicon atom bound to the iron(II) centre are subsequently transferred onto the carbonyl acceptor, instead remaining at the sterically inaccessible iron(II) atom throughout the catalytic cycle. A series of labelling, crossover and competition experiments as well as the use of a silicon-stereogenic hydrosilane as a stereochemical probe suggest that the iron(II) site is not directly involved in the hydrosilylation. Strikingly, it is the silyl ligand attached to the iron(II) atom that acts as a Lewis acid for carbonyl activation in this catalysis. The whole catalytic process occurs on the periphery of the transition metal. Computation of the new peripheral as well as plausible alternative inner and outer sphere mechanisms support the experimental findings.
URI: https://depositonce.tu-berlin.de//handle/11303/6931
http://dx.doi.org/10.14279/depositonce-6270
Issue Date: 2015
Date Available: 25-Oct-2017
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Sponsor/Funder: DFG, EXC 314, Unifying Concepts in Catalysis
Creative Commons License: https://creativecommons.org/licenses/by/3.0/
Journal Title: Chemical Science
Publisher: Royal Society of Chemistry
Publisher Place: Cambridge
Volume: 6
Issue: 12
Publisher DOI: 10.1039/c5sc02855h
Page Start: 7143
Page End: 7149
EISSN: 2041-6539
ISSN: 2041-6520
Appears in Collections:Fachgebiet Organische Chemie / Synthese und Katalyse » Publications
Fachgebiet Metallorganische Chemie und Anorganische Materialien » Publications

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