Rhodium carbene complexes as versatile catalyst precursors for Si–H bond activation

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dc.contributor.author Krüger, Anneke
dc.contributor.author Albrecht, Martin
dc.date.accessioned 2012-06-14T13:45:25Z
dc.date.available 2012-06-14T13:45:25Z
dc.date.copyright 2012 Wiley VCH en
dc.date.issued 2012-01-09
dc.identifier.citation Chemistry - A European Journal en
dc.identifier.uri http://hdl.handle.net/10197/3649
dc.description.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. en
dc.description.sponsorship Other funder en
dc.format.extent 594470 bytes
dc.format.mimetype application/pdf
dc.language.iso en en
dc.publisher Wiley-VCH en
dc.rights This is the author's version of the following article: Krüger, Anneke; Albrecht, Martin (2012) "Rhodium Carbene Complexes as Versatile Catalyst Precursors for Si–H Bond Activation". Chemistry - A European Journal: Volume 18, Issue 2, pages 652–658, which has been published in final form at http://dx.doi.org/10.1002/chem.201102197 en
dc.subject Rhodium en
dc.subject Silane activation en
dc.subject Siloxanes en
dc.subject Mesoionic complexes en
dc.subject Ligand cooperativity en
dc.subject Carbenes en
dc.subject.lcsh Carbenes (Methylene compounds) en
dc.subject.lcsh Cooperative binding (Biochemistry) en
dc.subject.lcsh Rhodium en
dc.subject.lcsh Siloxanes en
dc.subject.lcsh Activation (Chemistry) en
dc.title Rhodium carbene complexes as versatile catalyst precursors for Si–H bond activation en
dc.type Journal Article en
dc.internal.availability Full text available en
dc.status Peer reviewed en
dc.identifier.volume 18 en
dc.identifier.issue 2 en
dc.identifier.startpage 652 en
dc.identifier.endpage 658 en
dc.identifier.doi 10.1002/chem.201102197
dc.neeo.contributor Krüger|Anneke|aut| en
dc.neeo.contributor Albrecht|Martin|aut| en
dc.description.othersponsorship Swiss National Science Foundation en
dc.description.othersponsorship Sasol Ltd en
dc.description.othersponsorship Alfred Werner Foundation en
dc.description.admin ti, ke, sp, jo, li- TS 08.05.12 en

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