Smooth C(alkyl)-H Bond Activation in Rhodium Complexes Comprising Abnormal Carbene Ligands
|Title:||Smooth C(alkyl)-H Bond Activation in Rhodium Complexes Comprising Abnormal Carbene Ligands||Authors:||Krüger, Anneke
|Permanent link:||http://hdl.handle.net/10197/6664||Date:||14-Oct-2011||Abstract:||Rhodation of trimethylene-bridged diimidazolium salts induces the intramolecular activation of an alkane-type C–H bond and yields mono- and dimetallic complexes containing a formally monoanionic C,C,C-tridentate dicarbene ligand bound to each rhodium centre. Mechanistic investigation of the Calkyl–H bond activation revealed a significant rate enhancement when the carbene ligands are bound to the rhodium centre via C4 (instantaneous activation) as compared to C2-bound carbene homologues (activation incomplete after 2 days). The slow C–H activation in normal C2-bound carbene complexes allowed intermediates to be isolated and suggests a critical role of acetate in mediating the bond activation process. Computational modelling supported by spectroscopic analyses indicate that halide dissociation as well as formation of the agostic intermediate is substantially favoured with C4-bound carbenes. It is these processes that discriminate the C4- and C2-bound systems rather than the subsequent C–H bond activation, where the computed barriers are very similar in each case. The tridentate dicarbene ligand undergoes selective H/D exchange at the C5 position of the C4-bound carbene exclusively. A mechanism has been proposed for this process, which is based on the electronic separation of the abnormal carbene ligand into a cationic N–C–N amidinium unit and a metalla-allyl type M–C–C fragment.||Type of material:||Journal Article||Publisher:||Royal Society of Chemistry||Copyright (published version):||2011 The Royal Society of Chemistry||Keywords:||Rhodium complexes;Carbene ligands;C(alkyl)–H bond activation||DOI:||10.1039/C1DT11116G||Language:||en||Status of Item:||Peer reviewed|
|Appears in Collections:||Chemistry Research Collection|
Show full item record
Page view(s) 5012
This item is available under the Attribution-NonCommercial-NoDerivs 3.0 Ireland. No item may be reproduced for commercial purposes. For other possible restrictions on use please refer to the publisher's URL where this is made available, or to notes contained in the item itself. Other terms may apply.