Merging Pincer Motifs and Potential Metal-Metal Cooperativity in Cobalt Dinitrogen Chemistry: Efficient Catalytic Silylation of N to N(SiMe ).

Using a pyrazolate-bridged dinucleating ligand that provides two proximate pincer-type PNN binding sites ("two-in-one pincer"), different synthetic routes have been developed towards its dicobalt(I) complex 2 that features a twice deprotonated ligand backbone and two weakly activated terminal N substrate ligands directed into the bimetallic pocket. Protonation of 2 is shown to occur at the ligand scaffold and to trigger conversion to a tetracobalt(I) complex 4 with two end-on μ -bridging N ; in THF 4 is labile and undergoes temperature-dependent N /triflate ligand exchange. These pyrazolate-based systems combine the potential of exhibiting both metal-metal and metal-ligand cooperativity, viz. two concepts that have emerged as promising design motifs for molecular N fixation catalysts. Complex 2 serves as an efficient (pre)catalyst for the reductive silylation of N into N(SiMe ) (using KC and Me SiCl), yielding up to 240 equiv N(SiMe ) per catalyst.