The Tolman electronic parameter (TEP) and the metal–metal electronic communication in ditopic NHC complexes
Metadata
Show full item recordcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7053
comunitat-uji-handle3:10234/8639
comunitat-uji-handle4:
INVESTIGACIONThis resource is restricted
http://dx.doi.org/10.1039/c3dt32959c |
Metadata
Title
The Tolman electronic parameter (TEP) and the metal–metal electronic communication in ditopic NHC complexesDate
2013Publisher
Royal Society of ChemistryType
info:eu-repo/semantics/articleAbstract
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. [-]
Is part of
Dalton Transactions, 2013, 42Rights
© Royal Society of Chemistry 2014
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/restrictedAccess
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/restrictedAccess
This item appears in the folowing collection(s)
- QUIO_Articles [705]