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dc.contributor.authorGusev, Dmitry G.
dc.contributor.authorPeris, Eduardo
dc.date.accessioned2014-04-04T18:38:45Z
dc.date.available2014-04-04T18:38:45Z
dc.date.issued2013
dc.identifier.urihttp://hdl.handle.net/10234/89449
dc.description.abstractWhereas the electronic communication between metals in dimetallic organometallic compounds is often assessed through cyclic voltammetric measurements, we have found that the variations in the Tolman electronic parameter (TEP) can also be an alternative and effective way of determining this type of interaction. The TEP values of several (CO)3Ni–NHC–X systems with five different ditopic NHC ligand systems [triazolyldiylidene (A), bis(imidazolylidene) (B), benzobis(imidazolylidene) (C), cyclopenta[f,g]acenaphthylenebis( imidazolylidene) (D) and bis(imidazolidinylidene) (F)] were determined by means of DFT calculations. Based on these values, the electron-withdrawing character of the X metal fragments employed in this study was found to increase in the order IrCp(CO) → RhCl(COD) → Ni(CO)3 → Cr(CO)5 → RhCl(CO)2. We found that the degree of electronic interaction through the ditopic NHC ligands is the strongest in A, followed by B and F, while being weak in B and C. The TEP values and the quantitative analysis of the upper molecular orbitals of A and F and their (CO)3Ni–NHC–Ni(CO)3 complexes strongly suggest that the principal electronic interaction between the metal centres of the M–NHC–M’ complexes is of σ-type, via the delocalized HOMO and HOMO − 1 orbitals of the NHC ligands.ca_CA
dc.format.extent5 p.ca_CA
dc.format.mimetypeapplication/pdfca_CA
dc.language.isoengca_CA
dc.publisherRoyal Society of Chemistryca_CA
dc.relation.isPartOfDalton Transactions, 2013, 42ca_CA
dc.rights© Royal Society of Chemistry 2014ca_CA
dc.subjectTolman electronic parameter (TEP)ca_CA
dc.titleThe Tolman electronic parameter (TEP) and the metal–metal electronic communication in ditopic NHC complexesca_CA
dc.typeinfo:eu-repo/semantics/articleca_CA
dc.identifier.doihttp://dx.doi.org/10.1039/c3dt32959c
dc.rights.accessRightsinfo:eu-repo/semantics/restrictedAccessca_CA
dc.relation.publisherVersionhttp://pubs.rsc.org/en/Content/ArticleLanding/2013/DT/c3dt32959c#!divAbstractca_CA


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