A new reactivity pattern of heterodinuclear complexes [MnRe(CO)6(μ-S2CPR3)] with nBuLi/protonation and its electrochemistry properties investigation as structure and function models for the Fe-only hydrogenase active site

► Attack of nBuLi of MnRe complexes occurs with the formation of new (Bu)C-S bond. ► These non-iron complexes are shown to be electrocatalysts for H2 production. ► Two probable electrochemical mechanisms (EECC and ECCE) are proposed.