• carbenes;
  • donor– acceptor systems;
  • ligands;
  • NMR spectroscopy;
  • rhodium


A series of rhodium complexes, [Rh(cod)(NHC-Fx)(OH2)] (cod=1,5-cyclooctadiene; NHC=N-heterocyclic carbene), incorporating anionic N-heterocyclic carbenes with 2-tert-butylmalonyl backbones and 2,6-dimethylphenyl (x=0), 2,6-difluorophenyl (x=4), 2,4,6-trifluorophenyl (x=6), and pentafluorophenyl (x=10) N,N′-substituents, respectively, has been prepared by deprotonation of the corresponding zwitterionic precursors with potassium hexamethyldisilazide, followed by immediate reaction of the resulting potassium salts with [{RhCl(cod)}2]. These complexes could be converted to the related carbonyl derivatives [Rh(CO)2(NHC-Fx)(OH2)] by displacement of the COD ligand with CO. IR and NMR spectroscopy demonstrated that the degree of fluorination of the N-aryl substituents has a considerable influence on the σ-donating and π-accepting properties of the carbene ligands and could be effectively used to tune the electronic properties of the metal center. The carbonyl groups on the carbene ligand backbone provided a particularly sensitive probe for the assessment of the metal-to-ligand π donation. The ortho-fluorine substituents on the N-aryl groups in the carbene ligands interacted with the other ligands on rhodium, determining the conformation of the complexes and creating a pocket suitable for the coordination of water to the metal center. Computational studies were used to explain the influence of the fluorinated N-substituents on the electronic properties of the ligand and evaluate the relative contribution of the σ- and π-interactions to the ligand–metal interaction.