Electronic bond tuning with heterocyclic carbenes.
We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results.
Dipartimento di Chimica e Biologia, Università di Salerno, Via Ponte don Melillo, 84084 Fisciano, Italy.
Laura
L
Falivene
Lucia
L
Caporaso
Luigi
L
Cavallo
Heiko
H
Jacobsen