Merging Pincer Motifs and Potential Metal-Metal Cooperativity in Cobalt Dinitrogen Chemistry: Efficient Catalytic Silylation of N2 to N(SiMe3 )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 N2 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 μ1,2 -bridging N2 ; in THF 4 is labile and undergoes temperature-dependent N2 /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 N2 fixation catalysts. Complex 2 serves as an efficient (pre)catalyst for the reductive silylation of N2 into N(SiMe3 )3 (using KC8 and Me3 SiCl), yielding up to 240 equiv N(SiMe3 )3 per catalyst.