The Tolman electronic parameter (TEP) and the metal–metal electronic communication in ditopic NHC complexes
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http://dx.doi.org/10.1039/c3dt32959c |
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Título
The Tolman electronic parameter (TEP) and the metal–metal electronic communication in ditopic NHC complexesFecha de publicación
2013Editor
Royal Society of ChemistryTipo de documento
info:eu-repo/semantics/articleVersión de la editorial
http://pubs.rsc.org/en/Content/ArticleLanding/2013/DT/c3dt32959c#!divAbstractPalabras clave / Materias
Resumen
Whereas 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 ... [+]
Whereas 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. [-]
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Dalton Transactions, 2013, 42Derechos de acceso
© Royal Society of Chemistry 2014
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