Synthesis and properties of mononuclear group 10 alkoxy-biscarbene complexes.
The synthesis, isolation, and complete characterization (NMR and X-Ray diffraction techniques) of stable mononuclear (palladium and platinum) alkoxy-biscarbene complexes is reported. These compounds are easily accessible through stoichiometric transmetalation reactions from Fischer alkoxy-chromium(0) carbene complexes. By a combination of experimental (UV/Vis spectroscopy, cyclic voltammetry) and computational methods (DFT), the structure, bonding situation, and the electronic and redox properties of these complexes are studied. Although they have structures quite similar, their electronic properties strongly depend on the metal and also on the substitution in the aromatic rings in the aniline moieties. Electron-withdrawing groups stabilize the HOMO causing the shifting of the oxidation waves to lower anodic potentials in the corresponding cyclic voltammograms.
López-Alberca
María P
MP
Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, 28040 Madrid, Spain.
Mancheño
María J
MJ
Fernández
Israel
I
Gómez-Gallego
Mar
M
Sierra
Miguel A
MA
Torres
Rosario
R