Replacement of N-heterocyclic carbenes by N-heterocyclic silylenes at a Pd(0) center : Experiment and theory
2005
Via NMR-spectroscopy the relative reactivity of N-heterocyclic silylenes (NHSi) and carbenes (NHC) was studied. Reaction of sterically crowded bis-N-heterocyclic Pd(0) carbene complexes with free N-heterocyclic silylenes led to complete displacement of the N-heterocyclic carbene, which is unexpected knowing that usually a silylene is a weaker bound ligand compared to a carbene. High-level DFT calculations on a small model system and the experimentally used complexes confirm the experimental findings and indicate that steric interactions play an important role in the substitution reaction.
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