Dioxygen Splitting by a Tantalum(V) Complex Ligated by a Rigid, Redox Non-Innocent Pincer Ligand.

The reaction of TaMe₃ Cl₂ with the rigid acridane-derived trisamine H₃ NNN yields the tantalum(V) complex [TaCl₂ (NNN^cat )]. Subsequent reaction with dioxygen results in the full four-electron reduction of O₂ yielding the oxido-bridged bimetallic complex [{TaCl₂ (NNN^sq )}₂ O]. This dinuclear complex features an open-shell ground state due to partial ligand oxidation and was comprehensively characterized by single crystal X-ray diffraction, LIFDI mass spectrometry, NMR, EPR, IR and UV/VIS/NIR spectroscopy. The mechanism of O₂ activation was investigated by DFT calculations revealing initial binding of O₂ to the tantalum(V) center followed by complete O₂ scission to produce a terminal oxido-complex.