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Rhodium Carbene Complexes as Versatile Catalyst Precursors for SiH Bond Activation
Author(s) -
Krüger Anneke,
Albrecht Martin
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201102197
Subject(s) - carbene , heterolysis , chemistry , hydrosilylation , rhodium , silylation , catalysis , ligand (biochemistry) , silane , medicinal chemistry , bond cleavage , silanes , siloxane , hydrolysis , polymer chemistry , stereochemistry , photochemistry , organic chemistry , biochemistry , polymer , receptor
Rhodium(III) complexes comprising monoanionic C,C,C‐tridentate dicarbene ligands activate SiH bonds and catalyse the hydrolysis of hydrosilanes to form silanols and siloxanes with concomitant release of H 2 . In dry MeNO 2 , selective formation of siloxanes takes place, while changing conditions to wet THF produces silanols exclusively. Silyl ethers are formed when ROH is used as substrate, thus providing a mild route towards the protection of alcohols with H 2 as the only by‐product. With alkynes, comparably fast hydrosilylation takes place, while carbonyl groups are unaffected. Further expansion of the SiH bond activation to dihydrosilanes afforded silicones and polysilyl ethers. Mechanistic investigations using deuterated silane revealed deuterium incorporation into the abnormal carbene ligand and thus suggests a ligand‐assisted mechanism involving heterolytic SiH bond cleavage.