Publication
538
J.
Chem. Soc., Perkin Trans 2, 8, 1383-1388, 2001
DOI: 10.1039/b101228m |
|
|
Radical anions of carbenes and carbene homologues. DFT study and
preliminary experimental results
|
Laurence Pause, Marc Robert, Joachim
Heinicke and Olaf
Kühl
Laboratoire d'Electrochimie Moléculaire UMR CNRS 7591, Université Denis Diderot – Paris 7, 2 Place Jussieu,
75251 Paris Cedex 05, France,and Institut für Chemie und Biochemie, Ernst-Moritz-Arndt-Universität Greifswald, Soldmannstr. 16, D-17487 Greifswald, Germany
In the course of exploring the electronic properties and
chemistry of stable non-annelated and annelated heterocyclic
carbenes and carbene analogues (silylenes, germylenes and nitrenium
ions), we investigated ground state configurations of such
structures as well as their one-electron reduction by means of ab
initio calculations. We used a DFT approach, which proved to be
reliable for obtaining the geometries of the ground state molecules
and was thus employed for all calculations. The compounds
investigated are presented in Scheme 2. Injection of one electron
into these molecules leads to the formation of radical anions,
except for with cation 4a, which gives a neutral radical. For
all molecules, ground states are singlet states and comparison has
been made in terms of geometrical parameters with known experimental
structures and results obtained at the MP2 level of calculation.
These results, along with experimental dataon the reduction of
carbenes, nitrenium ions and germylenes obtained by cyclic
voltammetry, give some clues about their stability, properties and
potential redox activity. |