Selective Redox Activation of H2 or O2 in a [NiRu] Complex by Aromatic Ligand Effects

We present two closely related series of a [NiFe] hydrogenase analogue. Based on a [NiRu] core, these complexes demonstrate inactivity, H2 activation, or O2 activation depending only on the nature of the Ru-coordinated aromatic ligand. It is demonstrated that even small changes made to this aromatic ligand can modulate the catalytic activity of the complex. Structural, electrochemical, kinetic, and thermodynamic studies reveal that differences in activation and binding modes of the substrates, combined with differences in σ donation and lability of the aromatic ligands, result in abrupt changes in catalytic activity.