Selective Redox Activation of H<sub>2</sub> or O<sub>2</sub> in a [NiRu] Complex by Aromatic Ligand Effects
作者:Kyoungmok Kim、Takahiro Kishima、Takahiro Matsumoto、Hidetaka Nakai、Seiji Ogo
DOI:10.1021/om300833m
日期:2013.1.14
We present two closely related series of a [NiFe] hydrogenase analogue. Based on a [NiRu] core, these complexes demonstrate inactivity, H-2 activation, or O-2 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 a donation and lability of the aromatic ligands, result in abrupt changes in catalytic activity.