The structures of several complexes arising from the interaction between methylene and palladium and rhodium diformates were optimized through density functional calculations. For palladium, mono-, di-, and trimeric complexes were considered. The results obtained show that in all cases the most stable structures correspond to complexes in which methylene has inserted in one of the M-O bonds, while metal-carbene complexes are energy minima only for monomeric palladium diformate and for rhodium diformate. Trimeric palladium formate is thermodynamically stable upon fragmentation. However, when it reacts with methylene, fragmentation becomes favorable. The role of the resulting monomeric complex in the olefin cyclopropanation mechanism catalyzed by palladium dicarboxylates is discussed.
|Journal||European Journal of Inorganic Chemistry|
|Publication status||Published - 1 Jan 2000|
- Carbene complexes
- Carboxylato complexes
- Density functional calculations