How to tame a palladium terminal oxo

The isolation of terminal oxo complexes of the late transition metals promises new avenues in oxidation catalysis like the selective and catalytic hydroxylation of unreactive CH bonds, the activation of water, or the upgrading of olefins. While terminal oxo ligands are ubiquitous for early transition metals, well-characterized examples with group 10 metals remain hitherto elusive. In search for palladium terminal oxo complexes, the relative stability/reactivity of such compounds are evaluated computationally (CASSCF/NEVPT2; DFT). The calculations investigate only well-known ligand systems with established synthetic procedures and relevance for coordination chemistry and homogeneous catalysis. They delineate and quantify, which electronic properties of ancillary ligands are crucial for taming otherwise highly reactive terminal oxo intermediates. Notably, carbene ligands with both strong σ-donor and strong π-acceptor properties are best suited for the stabilization of palladium(ii) terminal oxo complexes, whereas ligands with a weaker ligand field lead to highly reactive complexes. Strongly donating ligands are an excellent choice for high-valent palladium(iv) terminal oxo compounds. Low coordinate palladium(ii) as well as high-valent palladium(iv) complexes are best suited for the activation of strong bonds.