The instability of [Fe-Fe]-hydrogenase and its synthetic models under aerobic conditions is an inherent challenge in their development as practical H-2 producing electrodes. The electrochemical oxygen reduction reaction of a series of synthetic model complexes of the [Fe-Fe] hydrogenase is investigated, and a dominant role of the bridgehead nitrogen in reducing the amount of partially reduced oxygen species (PROS), which is detrimental to the stability of these complexes, is discovered.