Light-promoted C-Cl bond-forming reductive elimination of a metal-metal bonded PdIII-PdIII complex.

ABSTRACT

The excited-state reductive elimination (RE) activities of a metal-metal bonded PdIII2 complex, [(2-phenylpyridyl)Pd(µ-acetate)Cl]2, are described. The C-Cl bond-forming RE reaction is accelerated by up to five orders of magnitude upon visible photoexcitation, which induces the Pd-Pd bond dissociation. This ligand field variation reduces the energy cost for intramolecular charge transfer (ICT) from coupling substrate to the metal center involved in the RE reaction. The correlation found between the ligand field and the RE activity indicates the ICT energy as a fundamental descriptor for RE reactions.