Holmes, J, Pask, CM and Willans, CE orcid.org/0000-0003-0412-8821 (2016) Chelating N-heterocyclic carbene-carboranes offer flexible ligand coordination to IrIII, RhIII and RuII: effect of ligand cyclometallation in catalytic transfer hydrogenation. Dalton Transactions, 45 (40). pp. 15818-15827. ISSN 1477-9226
Abstract
Imidazolium salts linked by an ethyl tether to closo-dicarbadodecaboranes were reacted with [IrCp*Cl2]2, [RhCp*Cl2]2 or [Ru(p-cymene)Cl2]2 in the presence of Ag2O to prepare complexes of the type [MCp*(NHC)Cl2] (M = Ir, Rh; NHC = N-heterocyclic carbene) or [Ru(p-cymene)(NHC)Cl2]. When the NHC contained an N-tBu substituent, C–H activation of the tBu and subsequent alkyl coordination was observed at Ir. Coordination of the closo-dicarbadodecaborane moiety to Ir was possible to give 7-membered metallacycles, coordinated through the carbenic carbon of the NHC and either a carbon atom or a boron atom of the carborane. Examination of the Ir complexes in the transfer hydrogenation of acetophenone to 1-phenylethanol reveals that cyclometallation of the carborane moiety is important for catalytic efficacy, indicating a bifunctional mechanism and involvement of the dicarbadodecaborane anion.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2016, The Royal Society of Chemistry. This is an author produced version of a paper published in Dalton Transactions. Uploaded in accordance with the publisher' self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 10 Aug 2016 12:29 |
Last Modified: | 21 Jul 2017 18:27 |
Published Version: | https://doi.org/10.1039/C6DT02079H |
Status: | Published |
Publisher: | Royal Society of Chemistry |
Identification Number: | 10.1039/C6DT02079H |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:103401 |