Skip to Main content Skip to Navigation
Journal articles

Ring-expanded iridium and rhodium N-heterocyclic carbene complexes: a comparative DFT study of heterocycle ring size and metal center diversity

Abstract : A new series of ring-expanded six- and seven-membered N-heterocyclic carbene precursors (re-NHCs) and their transition metal complexes were synthesized. The basic properties of the synthesized materials were investigated by density functional theory (DFT). The six- and seven-membered re-NHCs were synthesized in good yield via reaction of the corresponding alkyldibromides or alkyldiiodides with N,N′-bis-(2-phenylbenzene)formamidine in the presence of K2CO3 under aerobic conditions. Complexes, represented by the formula [ML1,2(COD)Cl] (where M = Ir or Rh and L is a ring-expanded N-heterocyclic carbene ligand), were synthesized in the presence of the corresponding free carbene and iridium or rhodium metal precursors in tetrahydrofuran. All new re-NHC complexes were characterized by different analytical techniques, including NMR spectroscopy, X-ray diffraction, UV spectroscopy and elemental analysis. According to molecular electrostatic potential calculations, the electrophilic properties of the complexes were aligned, from highest to lowest, as Ir-6-DiPh, Rh-6-DiPh and Ir-7-DiPh. The HOMO, LUMO and energy gaps of the complexes were calculated by DFT. On the basis of the DFT analysis, it can be predicted that Rh-6-DiPh is the most stable complex and Ir-7-DiPh is more reactive than Ir-6-DiPh. © 2017 Informa UK Limited, trading as Taylor & Francis Group.
Document type :
Journal articles
Complete list of metadatas

https://hal-univ-rennes1.archives-ouvertes.fr/hal-01515166
Contributor : Laurent Jonchère <>
Submitted on : Thursday, April 27, 2017 - 9:46:28 AM
Last modification on : Friday, July 10, 2020 - 4:10:16 PM

Identifiers

Citation

E.Ö. Karaca, M. Akkoç, E. Öz, S. Altin, V. Dorcet, et al.. Ring-expanded iridium and rhodium N-heterocyclic carbene complexes: a comparative DFT study of heterocycle ring size and metal center diversity. Journal of Coordination Chemistry, Taylor & Francis, 2017, 70 (7), pp.1270--1284. ⟨10.1080/00958972.2017.1287906⟩. ⟨hal-01515166⟩

Share

Metrics

Record views

173