Merging Pincer Motifs and Potential Metal–Metal Cooperativity in Cobalt Dinitrogen Chemistry: Efficient Catalytic Silylation of N(2) to N(SiMe(3))(3)

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(2) 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(1,2)‐bridging N(2); in THF 4 is labile and undergoes temperature‐dependent N(2)/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(2) fixation catalysts. Complex 2 serves as an efficient (pre)catalyst for the reductive silylation of N(2) into N(SiMe(3))(3) (using KC(8) and Me(3)SiCl), yielding up to 240 equiv N(SiMe(3))(3) per catalyst.