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Rhodium carbene complexes as versatile catalyst precursors for Si–H bond activation
Author(s)
Date Issued
2012-01-09
Date Available
2012-06-14T13:45:25Z
Abstract
Rhodium(III) complexes comprising monoanionic C,C,C-tridentate dicarbene ligands activate Si–H bonds and catalyse the hydrolysis of hydrosilanes to form silanols and siloxanes with concomitant release of H2. In dry MeNO2, selective formation of siloxanes takes place, while changing conditions to wet THF produces silanols exclusively. Silylethers are formed when ROH is used as substrate, thus providing a mild route towards the protection of alcohols with H2 as the only by-product. With alkynes, comparably fast hydrosilylation takes place, while carbonyl groups are unaffected. Further expansion of the Si–H bond activation to dihydrosilanes afforded silicones and polysilylethers. Mechanistic investigations using deuterated silane revealed deuterium incorporation into the abnormal carbene ligand and hence suggests a ligand-assisted mechanism involving heterolytic Si–H bond cleavage.
Sponsorship
Other funder
Other Sponsorship
Swiss National Science Foundation
Sasol Ltd
Alfred Werner Foundation
Type of Material
Journal Article
Publisher
Wiley-VCH
Journal
Chemistry - A European Journal
Volume
18
Issue
2
Start Page
652
End Page
658
Copyright (Published Version)
2012 Wiley VCH
Subject – LCSH
Carbenes (Methylene compounds)
Cooperative binding (Biochemistry)
Rhodium
Siloxanes
Activation (Chemistry)
Language
English
Status of Item
Peer reviewed
This item is made available under a Creative Commons License
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